Helium migration in alkali galliosilicate glasses

Helium migration has been measured for lithium, sodium, and potassium galliosilicate glasses. The results are compared with those from earlier studies of helium mobility in sodium and lithium aluminosilicate glasses. The concentration dependence of the helium permeability of glasses in all five glass-forming systems exhibits an abrupt change in behavior when the concentration of the intermediate oxide exceeds that of the alkali oxide. This effect appears to be related to changes in the effect of the intermediate oxide on the atomistic structure of the glass. Morphology effects have also been found to influence strongly, helium migration in the glasses containing lithium when the concentration of the intermediate oxide is relatively small.     

Towards the origin of the memory effect in oxide glasses

Glass samples with same composition and properties but different thermal histories can exhibit different behavior upon a subsequent heat-treatment, a phenomenon known as the memory effect. Generally, it is considered that the memory effect is due to nanoscale density fluctuation, which exists in all glasses and causes non-exponential relaxation with more than one relaxation time. Earlier, we studied the memory effect of various silica glasses and found that some pure silica glasses did not exhibit the memory effect while some silica glasses with higher impurity contents exhibited the memory effect. Based upon this finding, we suggested that the phenomenon originated from concentration fluctuation rather than density fluctuation. In this study, the memory effect in 6 mol% K₂O-94 mol% SiO₂ glass was investigated. The K₂O-SiO₂ glass system has a metastable immiscibility below the glass transition temperature and the chosen glass composition is the critical composition corresponding to the estimated critical temperature of the immiscibility boundary. Thus, it is expected that this glass composition would exhibit large super-critical concentration fluctuation, which increases with decreasing heat-treatment temperature. Density fluctuation, on the other hand, increases with increasing heat-treatment temperature. A much larger memory effect was observed at the lower heat-treatment temperature for the present glass. This result supports our earlier contention that the origin of the memory effect is composition fluctuation rather than density fluctuation.     

Structure and properties of Bi2O3---BaO---CuO glasses

The glass-forming region in the BiO_1.5---BaO---CuO system was determined, and the structure and crystallization of the glasses were investigated and compared to glasses containing CaO or SrO in place of BaO. It has been found that the glass-forming region in this system is wider than those in the BiO_1.5---CaO---CuO and BiO_1.5---SrO---CuO systems. BaBiO_2.77 was preferentially formed in the first stage of crystallization at all glass compositions. It is suggested that the Ba²⁺ ions may preferentially occupy the sites near BiO₆ octahedra, while the Ca²⁺ ions in BiO_1.5---CaO---CuO glasses may not have a site preference with respect to the BiO₆ octahedra.     

Structural relaxation in annealed hyperquenched basaltic glasses: Insights from calorimetry

The enthalpy relaxation behavior of hyperquenched (HQ) and annealed hyperquenched (AHQ) basaltic glass is investigated through calorimetric measurements. The results reveal a common onset temperature of the glass transition for all the HQ and AHQ glasses under study, indicating that the primary relaxation mechanism is activated at the same temperature regardless of the initial departure from equilibrium. The analysis of secondary relaxation at different annealing temperatures provides insights into the enthalpy recovery of HQ glasses.     

Physical properties of glasses containing several glass-forming oxides

Physical properties, such as dielectric loss, acoustic velocity and electrical conductivity of glasses containing several glass-forming oxides were measured at temperatures in the range from −200°C to 200°C. The relationships between the structure and properties of the glasses, and the change in coordination number of individual glass-forming cations in alkali-containing glasses were analysed. It is shown that the glasses containing several glass-forming oxides are characterized by an inhomogeneous structure.     

Glass formation and structure of Na2SSiO2 and Na2SB2O3 glasses

Glass-forming regions of the systems Na₂SSiO₂ and Na₂SB₂O₃ have been investigated in order to clarify whether Na₂S could be substituted for Na₂O in sodium silicate or borate glasses, and the results were interpreted in terms of the structures of silicate and borate glasses. No difference was found in the glass-forming range of SiO₂ content between the Na₂SSiO₂ and Na₂OSiO₂ systems, and the red color of Na₂SSiO₂ glasses suggests that the formation of polysulfides in the glass structure is probably due to the entrance of sulfur ions in the non-bridging sites of the glass network. On the other hand, not all of the sulfur added to the glass batches could be retained in the Na₂SB₂O₃ glasses and the amount remaining in the glass products changed depending upon the amount of sodium ions in the glasses. Only a trace of sulfur was observed in the glasses containing less than 13 mol% of Na₂S in the batches, but the sulfur content in the glasses increased steeply with sodium content up to 35 mol%, reached the maximum and then decreased slowly with sodium content. The insolubility of sulfur in the glasses with low sodium content was interpreted based on the compositional dependence of basicity of alkali-borate glasses, and the change in solubility of sulfur with sodium concentration was explained based on the well-known boron anomaly caused by the change in the coordination state of boron and on the formation of non-bridging oxygens or sulfurs in the glass structure.     

Structural analysis of some sodium and alumina rich high-level nuclear waste glasses

Sodium- and aluminum-rich high-level nuclear waste glasses are prone to nepheline (NaAlSiO₄) crystallization. Since nepheline removes three moles of glass-forming oxides (Al₂O₃ and SiO₂) per mole of Na₂O, the formation of this phase can result in severe deterioration of the chemical durability in a given glass. The present study aims to investigate the relationships between the molecular-level structure and the crystallization behavior of sodium alumino-borosilicate-based simulated high-level nuclear waste glasses with infrared spectroscopy (FTIR) and X-ray diffraction, respectively. The molecular structure of most of the investigated glasses comprise a mixture of Q² and Q³ (Si) units while aluminum and boron are predominantly present in tetrahedral and trigonal coordination, respectively. The increasing boron content has been shown to suppress the nepheline formation in the glasses. The structural influence of various glass components on nepheline crystallization is discussed.     

Optical and structural properties of new chalcohalide glasses

New class of chalcohalide glasses has been prepared in the GeS₂–In₂S₃–CsI system with regard to their potential non-linear properties. The study of glass-forming region was undertaken to select glassy compositions, which present high non-linear (NL) optical properties with a low two-photon absorption. Thermal analyses, structural examination by Raman spectroscopy, non-linear optical measurements were investigated as a function of CsI contents. Introduction of CsI has shifted the band-gap edge towards the blue region of the absorption optical spectrum and therefore has limited the two-photon absorption. Their NL refractive index n₂ are 60 times higher than silica glasses without any NL absorption. Moreover, second harmonic signal was observed in thermally poled samples similar to silica glass. However, this second order non-linearity is not temporally stable.     

Adequacy test of the fictive temperatures of silica glasses determined by IR spectroscopy

Adequacy of the fictive temperature determined by the IR spectroscopy method was examined for various silica glasses by measuring the extent of the memory effect. The IR method of fictive temperature measurement of silica glasses relies upon the assumption that a silica glass has a silica structural band with a unique wavenumber when it has a particular fictive temperature. Silica glasses with various impurities or added components such as Cl, F, and OH were given a cross-over heat-treatment and the extent of the resulting deviation of the wavenumber during the second stage heat-treatment at a constant temperature corresponding to the apparent fictive temperature of the sample was determined. Silica glasses containing high concentrations of water or fluorine exhibited distinct memory effects while glasses with low water concentration or Cl did not. These results seem to indicate that the main source of the memory effect in silica glasses is the composition fluctuation rather than density fluctuation. Thus, the IR method of determining the fictive temperature is adequate for high purity silica glasses even when the glass samples have unknown thermal history.     

Indentation-induced microhardness changes in glasses: Possible fictive temperature increase caused by plastic deformation

The microhardness around a large indentation was measured for different types of glasses. In soda-lime silicate glass, a typical normal glass, the region in the immediate vicinity of the indentation was found to exhibit a lower hardness than the region far removed from the indentation. In silica glass, a typical anomalous glass, the region in the immediate vicinity of a large indentation was found to exhibit a higher hardness than the region far removed from the indentation. Asahi less brittle glass, an intermediate glass between normal and anomalous glasses, was found to exhibit little change in hardness in the vicinity of the large indentation. These findings can be explained by a deformation-induced fictive temperature increase leading to a lower hardness for soda-lime silicate glass and a higher hardness for silica glass.     

Physical properties of barium borate glasses determined over a wide range of compositions

Barium borate glasses are reported over an extended glass-forming range from R=0.2 (16.7 mol% BaO) to R=2.0 (66.7 mol% BaO), where R is the molar ratio of barium oxide to boron oxide. The density, T_g (glass transition temperature), T_x (glass recrystallization temperature), and optical cutoffs were determined. These data were compared with structural models for the glasses based on nuclear magnetic resonance results of Greenblatt and Bray. The barium borate data were also compared with similar studies of lithium and lead borate glasses. Key results observed include: (1) the density trends are understandable in terms of the abundance of the basic borate groups with the fraction of tetrahedral borons being the most important single factor, and (2) the T_gs are anomalously high when compared to either the alkali or lead borate systems.     

Bulk metallic glasses based on ytterbium and calcium

We report the formation of a family of bulk metallic glasses (BMGs) based on rare earth element of ytterbium and alkaline earth element of calcium. The glass-forming ability, atomic packing density and corrosion behaviors of the BMGs show an extremum around the eutectic point with the change of the concentration of Yb and Ca.     

Behavior of Ag photodoping in sulfide bulk glasses

The relationship between Ag photodoping behavior and glass structure has been studied using various sulfide bulk glasses. The transmission measurement revealed that the photodoping rate increased with an increase of S concentration in Ge–S glasses and GeS₂–SbS₂ glasses, while the disappearance of Ag film was not be observed in Ge₄₀S₆₀ and Ga₂S₃-based glasses, which contain modifier ions. The correlation between photodoping rate and S–S bond content in a host glass was confirmed. From the point of view of the behavior of Ag photodoping, sulfide glasses were classified into two groups: (1) a covalent glasses containing S–S bonds and (2) an ionic glasses containing modified ions.     

Water diffusion in silicate glasses under natural weathering conditions: evidence from buried medieval stained glasses

In this study, ion-microprobe analyses of four samples of buried medieval stained-glasses are used to demonstrate that water penetrates into the matrix of pristine glasses at low temperatures, thereby showing that glass alteration is not only a surface process. The diffusion coefficients of water determined from concentration profiles of hydrogen are found to be correlated with the bulk polymerization state of the glass. This observation is discussed with respect to glass structure and implies that ionic exchange between hydrogen and network modifying metal cations is the major process responsible for glass hydration.     

Rare earth based bulk metallic glasses

Recently, the rare earth based bulk metallic glasses (REBMGs) have attracted increasing interest due to their unique properties and potential applications as functional glassy materials. These REBMGs display many fascinating properties such as heavy fermion behavior, thermoplastic properties near room temperature, excellent magnetocaloric effect, hard magnetism, and polyamorphism, all of which are of interest not only for basic research but also for metallurgy and technology. These characteristics and properties are ascribed to the unique electronic, magnetic and atomic structures of the REBMGs. In this review paper, the fabrication, glass-forming ability, polyamorphism, elastic, thermal, and physical properties are summarized and discussed. Owing to the unique electronic structure of rare earth elements, the electric and magnetic properties of the REBMGs are especially addressed. The works have implications for seeking novel metallic glasses with controllable properties and for understanding the nature of glass formation. The development of REBMGs as functional materials might promote and extend the commercial applications of metallic glasses.     

Structure and properties of silver phosphate glasses — Infrared and visible spectra

The infrared and visible spectra of glasses in the Ag₂OP₂O₅ glass-forming system were obtained. The infrared data were interpreted as indicating the presence of polymeric chains in these glasses. The partial covalent nature of the AgOP bond was discussed. A mixed NaPO₃AgPO₃ glass showed no unexpected bands in the infrared spectrum, again showing that silver is behaving in a manner similar to alkali metal ions in phosphate glasses. The shift in the absorption edge in the visible spectra of glasses of different Ag/P ratio was shown to arise from either an increase in the concentration of nonbridging oxygens with increasing silver content, or the presence of colloidal silver metal particles.     

Chromium doping of silicate glasses by field-assisted solid-state ion exchange

Field-assisted solid-state ion exchange (FASSIE) is a suitable way to dope glasses with metallic ions. This approach is a promising technique for the production of glass waveguides containing either bivalent or trivalent ions, allowing the doping of glass surfaces with multivalent ions which could not diffuse into the glass matrix by means of the usual thermal ion-exchange process in molten salt baths. In this paper, results on the diffusion of chromium in silicate glasses are presented. A metallic chromium film deposited on the top of the glass substrates was used as the metal ions supplier. The doped layers were investigated by secondary ion mass and Rutherford backscattering spectrometries, as well as by micro-Raman spectroscopy. Chromium entered the glass matrices for some hundreds of nanometers, depending on the process temperature and the applied electric field. Strong compositional modification of the treated glasses was detected, related to alkali and alkali-earth elements distribution. For field-assisted solid-state diffusion, borosilicate glasses seem to be more stable matrices than the soda-lime silicate ones.     

On the effect of glass composition in the dissolution of glasses by water

The dissolution rate in aqueous solution has been measured for three families of glasses of technological interest (borosilicates, aluminosilicates and lead-silicates). Borosilicates have been altered at a slightly basic pH (8–9), whereas the aluminosilicates and the lead-silicate glasses have been corroded in acidic solutions. In these conditions, silica is always less soluble than all other glass components. In each glass family, the effect of the silica content on the glass dissolution rate has been studied. The three series display a similar behavior as a function of the glass composition, namely a sharp increase of the dissolution rate with the content in soluble oxides. These experimental results have been explained in the framework of a Monte-Carlo simulation of glass dissolution. The simulations show that the fast extraction of the soluble species as compared to that of silica generates a porous surface layer, which becomes thicker and thicker when the percentage of soluble oxide increases in the glass. This increases the interface area between the glass and the solution, and consequently the dissolution rate in the same proportion. The numerical simulations reproduce quite well the experimental variations of the dissolution rates with glass composition.     

Properties and structure of AsTe glasses: (I). Glass-forming ability and related properties

AsTe glasses have been investigated for determining the molecular mechanisms of glass formation and of crystallization. Stable and homogeneous bulk glasses are prepared throughout the range of concentration from 20 to 65 at % As, by using an improved quenching method. GFA (glass-forming ability) is determined with respect to the rate of cooling. Density, microhardness, T_g and ΔC_p at T_g are measured in the whole range of glass formation. Finally a quantitative analysis of the kinetics of crystallization is carried out. It appears that most properties which involve molecular motions exhibit anomalies for As₄₀ Te₆₀ composition (As₂Te₃ is the unique definite compound of the system). So GFA shows a sharp depression for this critical composition; similarly enthalpy and kinetics of crystallization are drastically modified at As₄₀Te₆₀. For Te-rich glasses, crystallization occurs at low temperature by homogeneous nucleation with a small energy of activation. For As-rich glasses, crystallization occurs at much higher temperatures. Above 200°C it is controlled by growth with an high activation energy which indicates deep rearrangements of the relative positions of the atoms by chemical diffusion. A coherent analysis of all the data is developed which shows that important differences of local order exist between amorphous and crystalline states and also between the two well-distinct types of glasses we are dealing with. The aim of paper II is to determine these differences from diffraction data.     

DC conductivity and secondary structural relaxations in high-conducting Li glasses

In the course of investigating the mechanism of conductivity of fast-conducting, multicomponent lithium fluoroborate-type glasses, an isothermal drift in the conductivities has been found at temperatures so far below the normal glass transition ( 300°) that an origin in normal glass annealing effects appears improbable. Analysis of the 1st order kinetics of this relaxation in the temperature range 150–250°C yields an activation energy more than an order of magnitude less than that of the primary structural relaxation, suggesting the processunder observation is a secondary structural relaxation of the type frequently seen in polymer glasses.