A comparison of natural and experimental long-term corrosion of uranium-colored glass

The alteration features of historical U-colored glasses exposed to natural weathering for over 150 years were compared with the experimental alteration of similar glass with ～0.3 wt% of uranium using a long-term (up to 426 days) kinetic laboratory batch leaching test in deionized water. Two types of natural corrosion crusts were identified by a combination of SEM/EDS, HRTEM/SAED, EPMA and XRD: (i) formation of a leached layer (up to ～600 μm thick) depleted in alkalis and enriched in Si with stable concentration of U and Al and (ii) formation of lamellae depleted in alkalis, Si and U and enriched in Al. The presence of newly formed gibbsite (Al(OH)₃) and kaolinite (Al₂Si₂O₅(OH)₄) were confirmed in the second type of corrosion crust by HRTEM. Dissolution of the glass components including uranium was determined during the laboratory leaching test. Several μm thick alkali-depleted alteration zones with stable U content relatively enriched in Si and Al were formed on the glass surface. The PHREEQC-2 modeling also predicted the precipitation of secondary gibbsite and kaolinite in the late stages of the leaching. These phases may form especially when sufficient amounts of Al are available from the environment (e.g., soil). Furthermore, they provide surfaces for sorption and may, in some cases, affect the mobility of U ions released from the glass in dependence on pH and U speciation.     

Determination of the influence of TiO2 on the elastic properties of a mica based glass ceramic by ultrasonic velocity measurements

The influence of small amount (1 or 2 wt%) of TiO₂ additions and crystallization heat treatment on the elastic properties of a mica based glass ceramic have been investigated by ultrasonic velocity measurements. The mica based glass ceramic was prepared through controlled crystallization of a glass in the SiO₂, Al₂O₃, CaO, MgO, K₂O and F system. Evidences of TiO₂ acting as a nucleating agent in this system was demonstrated. The longitudinal and transversal wave velocities of the as-prepared glass and the mica based glass ceramic were measured by using 5 MHz probes at room temperature. Elastic properties namely; longitudinal modulus, Young’s modulus, bulk modulus, and shear modulus were calculated from the ultrasonic velocity values measured and density values obtained experimentally. It has been observed that small amount of TiO₂ additions caused a notable but not significant; however, the crystallization heat treatment had a profound effect on the elastic properties of the glass in the system studied.     

Synthesis and characterization of M2O–MgO–WO3–P2O5 (M = K, Rb, Cs) glass system

Transparent glasses of the composition M₂O–MgO–WO₃–P₂O₅ (M = K, Rb, Cs), corresponding to the crystalline phases of M₂MgWO₂(PO₄)₂, have been prepared and studied by Raman and IR spectroscopy as well as DTA. Moreover, the thermally stimulated depolarization and dc conductivity have been measured. The glass transition temperature is 797, 795 and 773 K for the K-, Rb- and Cs-containing glass, respectively. Raman and IR studies have shown that these glasses have very similar structure. The main building blocks are pyrophosphate groups, WO₆ octahedra and magnesium–oxygen polyhedra. The dc conduction in these glasses is controlled by hopping of small polarons. The potassium containing glass was shown to be very stable whereas the rubidium and cesium glasses have significantly higher tendency for crystallization and phase separation. It seems, therefore, that the potassium containing glass is a suitable material for the preparation of samples containing non-linear and ferroelectric nanocrystals of the K₂MgWO₂(PO₄)₂ phosphate.     

Aqueous alteration of five-oxide silicate glasses: Experimental approach and Monte Carlo modeling

The alteration behavior of glass comprising five oxides (61 ? x)SiO₂–17B₂O₃–18Na₂O–4CaO–xZrO₂ was studied during static leach tests in a buffer solution at 90 °C and with a glass-surface-area-to-solution-volume (SA/V) ratio of 15 cm^?1. The morphological evolution of altered glasses investigated by small-angle X-ray scattering (SAXS) exhibits a strong dependence with the zirconium content in the glass. The experiments were compared with modeling results using Monte Carlo simulation. The model has been improved to simulate the alteration kinetics and alteration layer morphology, considering zirconium atoms at coordination number 6. The simulations exhibit very good agreement with experimental results, showing relations between the alteration rate and the restructuring altered layer. The model is used to interpret experimental observations by proposing a porosity closure mechanism in the altered layer to account for the diminishing alteration rate. For high zirconium concentrations, the simulation highlights the existence of percolation pathways responsible for a complete alteration of the glass. Zirconium has a hardening effect that limits the dissolution of neighboring atoms; this effect is favorable in terms of the glass alteration kinetics, but by inhibiting silicon recondensation it prevents complete closure of the porosity and the glass is completely altered.     

Investigation of gel porosity clogging during glass leaching

A 5-oxide glass (62.5SiO₂, 16.6B₂O₃, 13.1Na₂O, 6.0CaO, 1.8ZrO₂) was leached at 90 °C at a high glass-surface-area-to-solution-volume ratio (SA/V = 80 cm^?1). Its dissolution rate diminished over time until it became unmeasurable. The alteration layer was characterized by ²⁹Si isotopic tracing in the leaching solution. ToF-SIMS elemental profiles showed that glass dissolution ceased due to clogging of the gel porosity at the gel/solution interface. One of the hypotheses proposed to account for the rate drop observed during borosilicate glass alteration is based on morphological changes in the alteration gel over time. Monte Carlo modeling of glass alteration, especially with simple glasses, indicates a clogging of the porosity on the external portion of the gel (near the solution/gel interface) after densification of the layer by silicon precipitation, but this phenomenon had never previously been directly observed experimentally. The initial results obtained by isotopic tracing provide new data that appears to confirm this hypothesis.     

Structure of titanophosphate glasses studied by X-ray and neutron diffraction

The structure of binary (TiO₂)_x(P₂O₅)_1−x glasses with x = 0.60, 0.65 and a ternary K₂O–TiO₂–P₂O₅ (KTP) glass were studied by X-ray and neutron diffraction. The experiments were performed at the high-energy beamline BW5 of the synchrotron DORIS (Hamburg/Germany) and at the GEM instrument of the neutron source ISIS (Chilton/UK). Gaussian fitting of well-resolved first-neighbor peaks in the correlation functions of the binary glasses with TiO₂ contents of 0.65 and 0.60 result in Ti–O coordination numbers of 5.65 ± 0.2 and 5.9 ± 0.2, respectively. Distorted TiO₆ octahedra and isolated PO₄ units form the glassy networks, with a small number of lower coordinated Ti sites for the 0.65 TiO₂ glass. For comparison, only TiO₆ octahedra are found for a ternary K₂O–TiO₂–P₂O₅ glass. The Ti–O coordination numbers are compared with a structural model where all oxygen atoms occupy sites in Ti–O–Ti, Ti–O–P or P–O–P bridges. The presence of three-coordinated oxygens must be assumed for the binary glasses, whereas a structure with nearly all oxygen atoms forming network bridges exists for the ternary KTP glass.     

Study of the alkaline environment in mixed alkali compositions by multiple-quantum magic angle nuclear magnetic resonance (MQ–MAS NMR)

45S5 Bioglasses of the composition 46.1 SiO₂–2.6 P₂O₅–26.9 CaO–(24.4 ? x) Na₂O–xMe₂O (Me = Li or K) have been investigated using MAS NMR and MQ–MAS NMR methods. The analysis of the ²⁹Si MAS NMR spectrum revealed two lineshapes whose chemical shift is consistent with two silica Q_n=2,3 species. The ³¹P MAS NMR spectrum reveals the effect of both Na and Ca ions. The chemical shift of the observed ³¹P signal is intermediate between those of Na₃PO₄ (near 10 ppm) and Ca₃(PO₄)₂ (near 3–0 ppm) species. The ²³Na MAS NMR spectra were observed in the alkali oxide composition: 24.4 Na₂O, 12.2 Na₂O–12.2 K₂O and 12.2 Na₂O–12.2 Li₂O. The substitution of Na with Li or K was done to determine the extend of alteration of the glass structure. This goal was best accomplished by ²³Na MQ–MAS NMR. The two-dimensional spectra revealed three sites in the 24.4 mol% Na₂O glass. These sites were not resolved in the 1D MAS NMR spectroscopy. In the mixed glasses, only two sites were obtained.     

Sol–gel synthesis and characterization of barium (magnesium) aluminosilicate glass sealants for solid oxide fuel cells

Solid oxide fuel cells (SOFC) correspond to efficient energy conversion systems coupled with low emissions of pollutants. In the aim to fabricate high temperature planar SOFC, glass and glass-ceramic sealants are developed to associate several criteria and properties : high thermal expansion (11.0 to 12.0 ? 10^? 6 K^? 1), high electrical resistance > 2 kΩ/cm², good thermochemical compatibility with the other active materials of the fuel cell, and stability under H₂ and H₂O atmospheres at an operation temperature of 800 °C for a long time. According to these requirements, new BAS (BaO–Al₂O₃–SiO₂) and BMAS (BaO–MgO–Al₂O₃–SiO₂) glass-ceramic sealants have been developed by sol–gel route which is a non-conventional process for such applications. By this soft chemistry process, we anticipate a decrease in the glasses processing temperature due to a better homogeneity between cationic precursors in the mixture and a more important reactivity of materials. Experimental results in terms of thermomechanical properties, thermal expansion coefficient, crystalline phase content, and microstructure were discussed. In particular, the influence of the %BaO on the thermomechanical properties of glass-ceramics was described. Changes in properties of glass-ceramics were closely related to the microstructure. The influence of MgO on glass processing temperatures, on the structure and on the microstructure is evaluated in order to confirm that these glass-ceramics are promising candidates to SOFC applications. So, after performing a systematic investigation to the various systems, the properties of suitable glass were proposed.     

Crystallization of KNbO3 in a B2O3 glass network

The ferroelectric material potassium niobate (KNbO₃) has a large number of exceptional electronic and optical properties with important technological applications. Due to the high preparation difficulties and costs of the single crystals, a considerable interest in the preparation of glass-ceramics with the KNbO₃ crystal phase exists. In this work we present the preparation of a glass, with the composition 40B₂O₃–40K₂O–20Nb₂O₅ (% mole), through the melt-quenching method and glass-ceramics obtained by controlled heat-treatments. The samples structure was analyzed using X-ray power diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy. KNbO₃ crystals were detected in the glass sample treated at 500 °C. For treatments at temperatures above 500 °C, other niobium-based crystal phases are present. The behavior of the heat-treatment temperature parameter, in the glass and glass ceramic structure, is discussed.     

The influence of CaF2 content on the physical properties and apatite formation of bioactive glass coatings for dental implants

This report details the physical properties, bioactivity and biocompatibility of manufactured glasses containing a range of calcium fluoride (CaF₂) concentrations. Compositions were based on the following system: SiO₂, CaO, Na₂O, K₂O, P₂O₅, ZnO and MgO, and in total seven glasses were synthesized using a melt–quench route. The ratio of the base compounds was kept constant, but had increasing CaF₂ concentrations (0.00, 2.44, 4.77, 9.11, 10.33, 11.53 and 13.00 mol%). Glasses were characterized using X-ray diffraction (XRD), differential scanning calorimetry (DSC) and dilatometery. Density was quantified according to Archimedes method and apatite formation tested following immersion in simulated body fluid (SBF) and Tris-buffer solution. Glass coatings were prepared by enamelling technique using 10 mm in diameter pure titanium disks. XRD demonstrates that all glasses are amorphous and that the sintering window, glass transition and softening temperatures decrease with increasing CaF₂ content. In contrast, thermal expansion coefficient and glass density increase with CaF₂ content. After 1 week immersion in SBF and Tris, XRD and Fourier transform infrared (FTIR) spectroscopy showed that the surfaces of all glasses underwent structural changes with evidence of surface apatite formation. Fluoride-electrode analysis indicates that the amount of fluoride released was proportional to the original CaF₂ content. The survival and growth of osteoblasts on the surface of these glasses is consistent with biocompatible characteristics.     

Diffusion coefficient of K+ in ion exchanged glasses calculated from the refractive index and the Vickers hardness profiles

The top faces of float glass samples were exposed to vapors resulting from the decomposition of KNO₃ at 565 °C for up to 32 h. X-ray dispersive spectra (EDS) show that K⁺ ions migrate into the glass. The K⁺ concentration profile was obtained and its diffusion coefficient was calculated by the Boltzmann–Matano technique. The mean diffusion coefficient was approximately 10 × 10⁻¹¹ cm² s⁻¹. It was observed that the refractive index and the Vickers hardness decrease with the depth (after the removal of successive layers), and their profiles were thus obtained. These profiles enabled the calculation of the diffusion coefficient of K⁺ through the Boltzmann–Matano technique, with mean results ranging between 6 × 10⁻¹¹ and 30 × 10⁻¹¹ cm² s⁻¹.     

Crystallization of barium magnesium phosphate glasses determined by differential thermal analysis and X-rays diffraction

The scope of this work is to determine the crystalline phases of devitrified barium magnesium phosphate glasses and the glass composition which presents the best resistance to crystallization. Barium magnesium phosphate glasses with composition xMgO · (1 ? x)(60P₂O₅ · 40BaO) mol% (x = 0, 0.15, 0.3, 0.4, 0.5, and 0.6) were analyzed by differential thermal analysis (DTA) to evaluate the thermal stability against crystallization, and X-ray diffraction (XRD) to identify the crystalline phases formed after devitrification. The glass transition temperature (T_g) increases as the MgO content increases. The maximum temperature attributed to the crystallization peak in the DTA curve (T_c) increases when x increases in the range 0 ? x ? 0.3, and it decreases for x > 0.3. The most thermally stable glass composition against crystallization is for x = 0.3. After the devitrification, the number of coexisting crystalline phases increases as the MgO content increases. For x = 0.3 there is the coexistence of γBa(PO₃)₂ and Ba₂MgP₄O₁₃ phases for devitrified glasses. The trend of the T_c is explained based on the assumptions of changes in the Mg²⁺ coordination number and the amphoterical features of MgO.     

Preparation of TiO2–Na2O glass by sol–gel method and structural characterization

The applicability of sol–gel process in glass formation of binary system, (100 − x)TiO₂–xNa₂O (x = 10, 20, 30), was investigated and the glasses were prepared successfully by the sol–gel process for the first time. The process of glass formation was checked by using X-ray diffraction measurement and DTA–TG analysis. In the baking step, a DTA peak related to the crystallization of gel was found. The short-range structure of glassified samples was studied by neutron scattering measurement. It is found from the results of neutron scattering measurement that the coordination number of O atom around Ti atom is about 4, and the O atoms around Ti atom form a planer square rather than a regular tetrahedron.     

Silver release from hydroxyapatite self-assembling calcium–phosphate glasses

The in vitro behavior of xAg₂O (100 ? x)[50P₂O₅ · 30CaO · 20Na₂O] glasses (0.14 ? x ? 20 mol%) is investigated in simulated body fluid (SBF) mainly with respect to bioactivity and silver ions release. In order to estimate the biodegradability and bioactivity, the samples were soaked in SBF, which has almost equal ions concentration to those of human blood plasma, and kept at 37 °C for fixed periods of time up to 18 days. After the fixed periods of time analyses were performed on the SBF solutions. Calcium and silver ions concentration of SBF after different soaking times of the glass samples were primarily examined. Conductivity data support the assumption that the released silver ions are reduced in SBF and their release is obstructed by growth of the bioactive layer on the glass surface. X-ray diffraction and infrared analysis attest the development on glass surface of a hydroxyapatite type layer.     

Preparation of transparent cobalt doped glass ceramic and application as saturable absorber Q switch for 1.54 μm Er-glass laser

Glass with composition of 51SiO₂–24.5Al₂O₃–23MgO–1.5K₂O doped with Co²⁺ ions was prepared by conventional melting method. The glass sample was heated at 900 °C for 360 min under atmosphere, and the powder XRD measurement showed that crystalline phase successfully precipitated in the sample. As is compared with standard JCPDS card, the crystalline phase identified as a mixture of zirconium titanate (ZrTiO₄) and one of the compounds of magnesium aluminum oxide. The crystallite size was confirmed by transmission electron microscope (TEM) observation; it could be estimated as 30 nm in diameter from the TEM image. Based on the area ratio of crystalline phase and residual glass phase, the precipitated crystallite phase volume ratio can be estimated to be not higher than 30% in the Co²⁺ doped glass ceramic sample. The absorption coefficient at 1.54 μm for transparent glass ceramic sample is clearly higher than that in base glass, which can be explained by the fact that Co²⁺ ions entered into the precipitated nano-sized crystal phase and led to higher absorption coefficient at 1.54 μm for tetrahedral coordinated Co²⁺ ion. Consequently, the Co²⁺ doped transparent glass ceramic sample with thickness of 0.35 mm was used as a saturable absorber for 1.54 μm Er-glass laser oscillation, and Q switched pulses with pulse energy of 40 mJ, pulse width of 42 ns, and peak power of 0.95 mW were shown in the experiments.     

Non-isothermal crystallization kinetic studies on MgO–Al2O3–SiO2–TiO2 glass

Thermal stability and crystallization kinetics of the glass 21% MgO, 21.36% Al₂O₃, 53.32% SiO₂ and 4.11% TiO₂ (mol%) has been studied using differential thermal analysis (DTA), dilatometry and X-ray diffraction (XRD). Glass in both bulk and frit forms were produced by melting in platinum crucible at 1600 °C for 1–2 h. From variation of DTA peak maximum temperature with heating rate, the activation energies of crystallization were calculated to be 340 kJ mol⁻¹ and 498 kJ mol⁻¹ for first and second crystallization exotherms, respectively. Crystallization of bulk glass was carried out at various temperatures and for different time durations in the range of 850–1000 °C. The influence of the addition of TiO₂ on the crystallization sequence of the glass was experimentally determined and discussed.     

Chemical durability and weathering resistance of canasite based glass and glass-ceramics

Classic composition 8.4Na₂O·5K₂O·10.8CaO·64SiO₂·10.5CaF₂·1.3Al₂O₃ (G1/GC1) and high silicon composition 7.6Na₂O·4K₂O·8.4CaO·71SiO₂·8CaF₂·1.0Al₂O₃ (G2/GC2) canasite-based glass and glass-ceramics were prepared, and the chemical durability and weathering of samples were studied with XRD, ICP-AES, SEM and optical microscopy. Interestingly, a kind of color fringe pattern caused by the acid leaching was directly observed on the glass ceramic surface under optical microscopy. The 20 day weight losses of glass and glass ceramic in acid (1 M HCl) and alkali (1 M NaOH/1 M Na₂CO₃) solution were measured. Accelerated weathering was used to demonstrate that increasing silicon content contributes to the weathering performance of glass and glass-ceramics. For different micro-structures and compositions, the weight loss of each glass and glass-ceramic is quite different. In general, through increasing the network interconnectivity of residual glass network and suppressing the crystallization of the less durable canasite phase, the addition of SiO₂ (from 60 mol% to 71 mol%) enhanced the chemical durability of canasite-based glass and glass ceramic relatively under acid, alkali and weathering conditions.     

Multicomponent phosphate invert glasses with improved processing

Owing to their structure of small phosphate units, phosphate invert glasses have high crystallisation tendencies, which make processing of the melt challenging. The aim was to improve their processing by (1) increasing the number of glass components and (2) incorporating intermediate oxides (TiO₂, MgO and ZnO). Glasses (P₂O₅–CaO–MgO–Na₂O) were produced by a melt-quench route. In series 1, TiO₂ was partially substituted for Na₂O, and the number of components was increased by partially substituting strontium for calcium, zinc for magnesium and potassium for sodium on a molar base. In series 2, the MgO + ZnO content in the multicomponent glass was varied between 0 and 20 mol% in exchange for CaO + SrO. Differential scanning calorimetry showed a significant increase of the processing window in the multicomponent glasses, explained by an increased energy barrier for crystallisation owing to increased entropy of mixing. The MgO + ZnO content also significantly improved the processing window from 117 K (0 mol% MgO + ZnO) to 185 K (20 mol%), owing to their large field strength. These results show that the processing of phosphate invert glasses for biomedical applications can be improved significantly by incorporating ions such as strontium or zinc which are also known to have therapeutic effects.     

Influence of the partial substitution of CaO with MgO on the thermal properties and in vitro reactivity of the bioactive glass S53P4

The influence of up to 4 mol% substitution of MgO for CaO on the properties of the bioactive glass S53P4 was studied. Thermal analysis, hot stage microscopy and X-ray diffractometry were utilized to measure the thermal properties and the crystallization characteristics of the glasses. The in-vitro bioactivity was measured by immersing the glasses for 4 h to one week in simulated body fluid. The formation of silica rich and hydroxyapatite layers was assessed from FTIR spectra analysis and SEM images of the glasses surface. Increasing substitution of MgO for CaO decreased the glass transition, the onset and endset of melting and the fusion temperatures. The activation energies for glass transition and crystallization also decreased from (790 ± 30) to (407 ± 30) kJ/mol and from (283 ± 30) to (145 ± 30) kJ/mol, respectively, indicating a decrease in bond length and an increase in bond strength with progressive MgO at the expense of CaO. All glasses dissolved identically in SBF during the first 24 h of immersion with subsequent formation of hydroxyapatite at the grain surfaces. The thickness of the surface layers decreased with increasing MgO content. For longer duration of immersion, the glasses with the highest MgO contents exhibited a slower reaction tendency, with simulated body fluid, than the Mg-free glass. These changes in the glass structure and in-vitro properties may be of interest for products from bioactive glasses with large surface area to volume ratio.     

X-ray absorption spectroscopy and high-energy XRD study of the local environment of copper in antibacterial copper-releasing degradable phosphate glasses

Phosphate-based glasses of the general formula Na₂O–CaO–P₂O₅ are degradable in an aqueous environment, and therefore can act as antibacterial materials through the inclusion of ions such as copper. In this study, CuO and Cu₂O were added to Na₂O–CaO–P₂O₅ glasses (1–20 mol% Cu) and X-ray absorption spectroscopy (XAS) and high-energy X-ray diffraction (HEXRD) used to probe the local environment of the copper ions. Copper K-edge X-ray absorption near-edge structure (XANES) spectra confirm the oxidation state of copper to be predominantly 2+ in all samples regardless of which copper oxide was used in the preparation. The XANES results suggest the structural environment of copper to be octahedral with respect to oxygen in all samples. The HEXRD results yield a Cu–O nearest-neighbour distance of 1.98 Å and associated coordination number of approximately six, both consistent with octahedral coordination. Analysis of the extended X-ray absorption fine structure (EXAFS) data also yields structural parameters consistent with copper in an octahedral environment. The HEXRD and EXAFS results reveal a Cu–P distance of 3.13 Å, which confirms that the copper ions are coordinated within the phosphate glass network and not phase-separated in domains of copper oxide.