Electrical conductivity and relaxation in mixed alkali tellurite glasses

The authors have reported the electrical conductivity and the conductivity relaxation in mixed alkali tellurite glasses of compositions of 70TeO2-xNa2O-(30-x)Li2O in the frequency range from 10 Hz to 2 MHz and in the temperature range from room temperature to just below the glass transition temperature. They have analyzed the relaxation data in the framework of different models. They have observed the mixed alkali effect in the dc and ac conductivities, the crossover frequency, and the conductivity relaxation frequency as well as in their respective activation energies in these glasses. They have also observed the mixed alkali effect in the decoupling index. The scaling property of the modulus spectra of these mixed alkali glasses shows that the conductivity relaxation in the mixed alkali tellurite glasses is independent of temperature but depends on the glass compositions.     

In vitro degradability and bioactivity of mesoporous CaO-MgO-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-SiO<Subscript>2</Subscript> glasses synthesized by sol–gel method

Two glasses of the CaO-MgO-P₂O₅-SiO₂ system with different MgO contents (0 and 10 mol%, respectively) have been synthesized by sol–gel method. The degradation of glass samples was evaluated through the weight loss in the tris-(hydroxymethyl)-aminomethane and hydrochloric acid (Tris–HCl) buffer solution, and the in vitro bioactivity was assessed by determining the changes in surface morphology and composition after soaking in a simulated body fluid. Formation of the apatite-like layer on glasses surface was studied by means of X-ray diffraction, Fourier-transform infrared, scanning electron microscopy. Results indicate that, with the partial substitution of MgO for CaO in glass composition, the glass degradation decrease and the formation of apatite-like layer is delayed. Furthermore, it is observed that the glass bioactivity is relative to its dissolution, and the effects of MgO on glass degradability and bioactivity may be attributed to the influence of ionic field strength and distinct bonding configuration of glass.     

Impact of network topology on cationic diffusion and hardness of borate glass surfaces

The connection between bulk glass properties and network topology is now well established. However, there has been little attention paid to the impact of network topology on the surface properties of glass. In this work, we report the impact of the network topology on both the transport properties (such as cationic inward diffusion) and the mechanical properties (such as hardness) of borate glasses with modified surfaces. We choose soda lime borate systems as the object of this study because of their interesting topological features, e.g., boron anomaly. An inward diffusion mechanism is employed to modify the glass surface compositions and hence the surface topology. We show that accurate quantitative predictions of the hardness of the modified surfaces can be made using topological constraint theory with temperature-dependent constraints. Experimental results reveal that Ca(2+) diffusion is most intense in glasses with lowest BO(4) fraction, whereas Na(+) diffusion is only significant when nonbridging oxygens start to form. These phenomena are interpreted in terms of the atomic packing and the local electrostatic environments of the cations.     

Essais en autoclave de flacons de verre a usage pharmaceutique

The behaviour in autoclave testing (French Pharmacopoeia) of bottles made from borosilicate glass (class I), surface-treated soda-lime glass (class II) and untreated sodalime glass (class III) is compared. Several (6–10) elements were determined by wet-chemical methods in the autoclave solutions. The results are compared with surface data obtained by secondary-ion mass spectrometry (SIMS) before and after the autoclaving. The SIMS profiles show that autoclaving of class I and II glasses scarcely modifies the surfaces of these glasses whereas class III glass is attacked to a depth of ca. 40 nm. The surface treatment with ammonium sulphate is shown to be efficient in reducing the diffusion of ions from the glass surface to the leaching solution. The validity of the hydrolytic resistance test given in the French Pharmacopoeia is confirmed.     

Lead determination in glasses by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been used to determine the lead content of different types of lead silicate glasses commercially designed as sonorous glass (which contain ∼ 10 wt.% PbO); crystal glass (with at least 24 wt.% PbO) and superior crystal glass (with at least 30 wt.% PbO). Seven different types of glass samples were selected, including historic-original, model and commercially available. The selected samples were artificially weathered under neutral, acid and alkaline attack. Analysis by LIBS was carried out in vacuum under excitation at 266 nm and results were compared with those obtained by conventional techniques used for glass characterization. Composition of the bulk glasses was analyzed by XRF (X-ray fluorescence) and the corroded surfaces were characterized by SEM/EDX (scanning electron microscopy/energy dispersive X-ray microanalysis). A linear correlation was obtained between the intensity of selected Pb lines in the LIB spectra and the PbO content. The effect of corrosion could be characterized by comparing successive LIB spectra recorded on the same area; acid attack resulted in a decrease of PbO, CaO and Na₂O content in the surface with respect to the bulk of the sample, while minor changes in the composition were noticed under alkaline attack. These results show LIBS as a useful technique to classify the different types of lead glasses by their lead content and to determine and asses the degree and type of corrosion.     

Atomic force microscopy study of salivary pellicles formed on enamel and glass in vivo

This study was performed to evaluate the use of atomic force microscopy (AFM) in examining the surface of the adsorbed layer of salivary proteins (salivary pellicle) formed in vivo on dental enamel and glass surfaces. Enamel and glass test pieces were attached to the buccal surfaces of the upper first molar teeth in two adults using removable intraoral splints. The splints were carried intraorally over periods ranging from 10 min to1 h. Using the contact mode of AFM, pellicle structures could be recognised on intraorally exposed specimens compared to nonexposed enamel and glass surfaces. The surface of the adsorbed salivary pellicle was characterised by a dense globular appearance. The diameter of the globulelike protein aggregates adsorbed onto enamel and glass varied between 80 and 200 nm and 80 and 150 nm, respectively. The structure of the adsorbed protein layer was clearly visible on glass surfaces, even though minor differences in the protein layer between glass and enamel specimens were observed. This study indicates that AFM is a powerful tool for high-resolution examination of the salivary pellicle surface structure in its native (hydrated) state. AFM avoids artefacts due to fixing, dehydration and sputter-coating which occur with scanning electron microscopic analyses. Received: 29 November 2000 Accepted: 14 December 2000     

Laser induced breakdown spectroscopy for analysis and characterization of degradation pathologies of Roman glasses

The feasibility and possibilities of laser induced breakdown spectroscopy (LIBS) in the full study of non-destructible historic glasses have been explored in the present work. Thirteen Roman glass samples, including seven entire glass beads, from the ancient town of Augusta Emerita (SW Spain) were characterized by LIBS in combination with other conventional techniques, such as scanning electron microscopy/energy dispersive X-ray spectrometry, X-ray fluorescence and ultraviolet–visible spectrophotometry. LIBS stratigraphic analysis, carried out by the application of successive laser pulses on the same spot, has been mainly targeted at characterizing particular features of non-destructible historic glasses, such as bulk chemical composition, surface degradation pathologies (dealkalinization layers and deposits), chromophores, and opacifying elements. The obtained data demonstrate that LIBS can be a useful and alternative technique for spectroscopic studies of historical glasses, especially for those conserved under burial conditions and when it deals with studying non-destructible samples.     

Electrokinetic Characteristics of Porous Glasses in Solutions of Sodium and Iron(III) Chlorides

The structural (structural resistance coefficient, bulk porosity, average pore radius, and specific surface area) and electrokinetic (surface conductivity and electrokinetic potential) characteristics of high-silica micro- and macroporous glasses produced from two-phase sodium borosilicate glass have been compared in solutions of an indifferent electrolyte (sodium chloride) and iron(III) chloride containing iron ions, which have a high specificity to silica surfaces. It has been shown that, in the presence of iron ions, the electrokinetic behavior of porous glasses is governed by two factors. First, the superequivalent adsorption of these ions in the Stern layer leads to positive values of the electrokinetic potential, and, second, their mobility in the pore space decreases, thereby resulting in the appearance of equilibrium solution concentration ranges, in which the specific conductivity of a pore solution becomes lower than that of a free solution.     

The effect of changing the TiO2 content (0-6%) on the structure and thermal evolution of glasses obtained from porphyric sands and dolomite

Glasses have been obtained from mixtures of porphyric sands and dolomite. The influence of changes in the TiO₂ content (0-6%) on the glass structure and the formation of crystalline phases on reheating has been studied. The experimental results suggest that in the studied system TiO₂ promotes glass-in-glass phase separation and plays the role of a nucleating agent. The activation energy for crystal growth, E_C = 486 kJ mol⁻¹, and the Avrami parameter (m = 1) have been evaluated by means of thermoanalytical techniques in the case of the base glass (no TiO₂ added). The value of the Avrami parameter (m = 1) agrees well with SEM observations of dendritic crystal growth from surface nuclei. In the other glasses, lath-like crystals were observed, the microstructure being finer the greater the TiO₂%. The first addition of TiO₂ (2%) gives, on quenching, a partially devitrified product; subsequent additions of titania, surprisingly, allow glasses to be formed more easily. The experimental results suggest that Na₂O and K₂O, present in the porphyric sands and therefore in the glasses (to a total amount of ≈ 5.6%), segregate preferentially into the titania-rich phase with respect to MgO. Taking into account that Na₂O and K₂ are useful in lowering the liquidus temperature of glasses but are known to have a negative effect on the mechanical properties, this can be important in the production of glass ceramics.     

Dynamics of lithium ions in calcium bismuthate glasses

Ion transport in Li(2)O-CaO-Bi(2)O(3) glasses has been studied in the frequency range from 10 Hz to 2 MHz and in the temperature range from 293 to 543 K. The variation of the dc conductivity and the activation energy of these glasses with composition have been compared with those of binary lithium bismuthate glasses. It has been observed that the introduction of CaO in small amount does not effect the dc conductivity and the corresponding activation energy, but the larger amount of CaO changes them to some extent. The frequency-dependent conductivity has been studied using both conductivity and modulus formalisms. The values of the nonexponential parameter and frequency exponent are found to differ for the Li(2)O-CaO-Bi(2)O(3) glasses from those for the binary Li(2)O-Bi(2)O(3) glasses. The concentration of mobile Li(+) ions does not change appreciably with the change in the Li(2)O as well as CaO content in the compositions. The increasing amount of CaO in the glass compositions for fixed Li(2)O content points out that CaO dilates the glass network, enhancing the migration of Li(+) ions.     

Facilitated tip-positioning and applications of non-electrode tips in scanning electrochemical microscopy using a shear force based constant-distance mode

In scanning electrochemical microscopy (SECM) a microelectrode is usually scanned over a sample without following topographic changes (constant-height mode). Therefore, deconvolution of effects from distance variations arising from non-flat sample surface and electrochemical surface properties is in general not possible. Using a shear force-based constant distance mode, information about the morphology of a sample and its localized electrochemical activity can be obtained simultaneously. The setup of the SECM with integrated constant-distance mode and its application to non-flat or tilted surfaces, as well as samples with three-dimensional surface structures are presented and discussed. The facilitated use of non-amperometric tips in SECM like enzyme-filled glass capillaries is demonstrated.     

The application of highly soluble amine-terminated aromatic polyimides with pendent tert-butyl groups as a tougher for epoxy resin

Polyimides(PIs) with various molecular weights synthesized via the reaction of aromatic diamine monomer containing tert-butyl groups with aromatic dianhydride were highly soluble in common organic solvents and some epoxy resins at room temperature. These PIs can be incorporated in the absence of organic solvent into epoxy resin E51 with the loading below 2 wt% forming EP-PI composites. No phase separation is observed by SEM on cryogenically fractured surfaces of EP-PI composites. The PI can improve mechanical properties, especially impact strength. Adding 2 wt% PI-1.5W, the impact strength reaches to 55 k J/m2 with the increase in tensile and flexural strengths by 14% and 3%, respectively. SEM analyses for the fracture surface suggest that PI reduces the crosslink density, improves the plasticity of epoxy resin and changes the mode of fracture from fragile to ductile. Moreover, the glass transition temperature of EP-PI composites was found to increase to a significant extent.     

The kinetics of phase transitions in vitreous chalcogenide semiconductors As10.2Se89.8 and As9Se90Bi in early stage of physical ageing process

The kinetics of glass transition in selenide glasses As_10.2Se_89.8 and As₉Se₉₀Bi in early stage of physical ageing process has been investigated by parallel differential scanning calorimetry (DSC) and exoelectron emission (EEE). It has been found that the glass transition process occurring in investigated glasses is evidenced by peaks on EEE intensity and DSC curves. Admixture of bismuth causes a distinct lowering of the temperature of glass transitions process both in the surface layer and in the volume. The addition of Bi causes a decrease in the value of the activation energy for glass transition process in both the volume and in the surface layer, thus reducing the thermal stability of investigated glasses. Physical ageing in Se-rich chalcogenide glasses leads to a significant increase of endothermic peak area A, temperature of glass transition T _g and decrease of the activation energy value E. All these effects are strongly dependent on glass composition.     

Raman spectroscopic study on archaeological glasses in Thailand: ancient Thai glass

Glasses have been used as ornamental and decorative objects in Thailand for several hundred years as seen in archaeological artifacts, such as glass beads found throughout the regions. Decorative glasses can generally be seen as architectural components in Buddhist temples and old-styled palaces. They came in various colors ranging from transparent to amber, blue, green and red of different shades and tones. Fragments of archaeological glass samples were characterized for the first time using Raman spectrophotometer with the aim of obtaining information that would lead to the identification of the glass samples by means of laser scattering. The samples were also investigated using other techniques, such as proton induced X-ray emission spectroscopy, scanning electron microscopy cooperated with energy dispersive X-ray fluorescence spectrometer and synchrotron radiation to induced X-ray fluorescence. The results showed that they were mostly lead-silica based glasses whose colors were induced by metal ions. The differences in chemical compositions were confirmed by Raman signature spectra.     

碘化亚铜微晶掺杂硅酸盐玻璃的制备及其光学性质

采用可分相的Na2O－Al2O3－B2O3－SiO2系为基础玻璃，以CuO／SnO、NaI为原料分别引入Cu＋、I－，成功地制备出CuI激晶掺杂硅酸盐玻璃．通过X射线粉末衍射（XRD）和高分辨透射电镜（HRTEM）分析观察到玻璃中的晶相和微晶的分布情况；由玻璃的室温透射光谱研究了玻璃的热处理条件与光吸收性的关系．实验发现，该玻璃对Nd：YAG激光器腔内自由振荡具有脉定压缩效应．     

Influence of particle size on the crystallization process and the bioactive behavior of a bioactive glass system

Bioactive glasses have attracted considerable interest in recent years, due to their technological application, especially in biomaterials research. Differential scanning calorimetry (DSC) has been used in the study of the crystallization mechanism in the SiO₂–Na₂O–CaO–P₂O₅ glass system, as a function of particle size. The curve of the bulk glass presents a slightly asymmetric crystallization peak that could be deconvoluted into two separate peaks, their separation being followed in the form of powder glasses. Also, a shift of the crystallization peaks to lower temperatures was observed with the decrease of the particle size. FTIR studies – that are confirmed by XRD measurements – proved that the different peaks could be attributed to different crystallization mechanisms. Moreover, it is presented the bioactive behavior of the specific glass as a function of particle size. The study of bioactivity is performed through the process of its immersion in simulated human blood plasma (simulated body fluid, SBF) and the subsequent examination of the development of carbonate-containing hydroxyapatite layer on the surface of the particles. The bioactive response is improved with the increase of the particle size of powders up to 80 μm and remains almost unchanged for further increase, following the specific surface to volume ratio decrease.     

Comparison of the adsorption orientation for 2-mercaptobenzothiazole and 2-mercaptobenzoxazole by SERS spectroscopy

In this study, the adsorption orientation for 2-mercaptobenzothiazole (MBT) and 2-mercaptobenzoxazole (MBO) on to silver mirror and silver sol substrates have been studied by surface enhanced Raman scattering (SERS). The MBT and MBO were chemisorbed on both silver mirror and silver sol after deprotonation with a tilted orientation to the silver surfaces. The surface enhanced properties of MBT and MBO showed that the substrate of silver mirror was superior to the sliver sol. The SERS spectra of MBT and MBO revealed that both of the MBT and MBO were adsorbed on silver surfaces strongly by a common sulfur molecule and a sulfur atom from MBT and an oxygen atom from MBO. Therefore, the adsorption orientation of MBT and MBO was little tilted perpendicularly to the silver surfaces. The adsorption geometry did not undergo any significant changes in acidic and basic solutions. It showed that the adsorption orientation for MBT and MBO were stable in the both solutions.     

Influence Of Zro2 on The Physicochemical Properties of Phosphate-Based Glasses and Glass Ceramics

Abstract

Phosphate-based bioactive glasses and their glass ceramics for 47P₂O₅– (30.5)CaO–(22.5 ? x)Na₂O–xZrO₂ for different ZrO₂ contents (x = 0, 1.5, 3.0, 4.5, and 6.0 mol%) were prepared through melt quenching and controlled heat treatment procedures. The amorphous nature of glasses and the presence of crystalline phases in glass ceramics were studied by means of X-ray diffraction (XRD) studies. The density, molar volume, ultrasonic velocities, attenuation, elastic constants, and microhardness of glass and glass ceramics were used to study the structural changes. The formation of hydroxyapatite layer on the surface of glasses and glass ceramics after immersion in simulated body fluid (SBF) was explored through XRD, Fourier transform infrared (FTIR), and scanning electron microscopy (SEM) analyses. The results indicate that the added ZrO₂ increases the crosslink density of glasses, resulting in network stability, and also induces the formation of an apatite layer on the surface of glasses.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Spectral analysis of Cu(2+): B(2)O(3)--ZnO--PbO glasses

A new series of heavy metal oxide (PbO) based zinc borate glasses in the chemical composition of (95-x)B(2)O(3)-5ZnO-xPbO (x=10, 15, 20, 25, 30, 35, 40, 45 and 50 mol%) have been prepared to verify their UV filtering performance. Both direct and indirect optical band gaps (E(opt)) have been evaluated for these glasses. For a reference glass of 45B(2)O(3)-5ZnO-50PbO, refractive indices at different wavelengths are measured and found the results satisfactorily correlated with the theoretical data upon the computation of Cauchy's constants of A=1.766029949, B=159531.024 nm(2) and C=-1.078 x 10(10) nm(4). Measurements concerning X-ray diffraction (XRD), FT-IR, differential scanning colorimeter (DSC) profiles have been carried out for this glass. The FT-IR profile has revealed that the glass has both BO(3) and BO(4) units. From DSC thermogram, glass transition temperature (T(g)), crystallization temperature (T(c)) and melting temperature (T(m)) have been located and from them, other related parameters of the glass have also been calculated. Visible absorption spectra of 45B(2)O(3)-5ZnO-(50-x)PbO-xCuO (x=0. 1, 0.2, 0.5 and 1.0 mol%) have revealed two absorption bands at around 400 nm ((2)B(1g)-->(2)E(g)) and 780 nm ((2)B(1g)-->(2)B(2g)) of Cu(2+) ions, respectively. Emission bands at 422 and 512 nm are found for the 1 mol % CuO doped glass with excitations at 306 and 332 nm.     

Glasses in the CuNbOF<Subscript>5</Subscript>-BaF<Subscript>2</Subscript> and CuNbOF<Subscript>5</Subscript>-PbF<Subscript>2</Subscript> systems

Nonhygroscopic, colored glasses have been synthesized in the CuNbOF₅-BaF₂ and CuNbOF₅-PbF₂ systems proceeding from crystals of the complex compound CuNbOF₅ · 4H₂O. The glasses have been studied structurally and thermally. The crystallization resistance of the glasses has been studied as a function of glass composition. Lead difluoride glasses are more stable than barium difluoride glasses of the same composition. These glasses have lower glass-transition temperatures than the binary glasses formed in the NbO₂F-BaF₂ system. The glass structure is built of Nb(O,F)₆ polyhedra, which are linked in glass networks through oxygen bridges. Modifier cations influence both the structure of glass networks and the linkage of polyhedra.