A neutron small angle scattering study of SiO2Na2 O glasses

The first results obtained by small-angle neutron scattering (SANS) study of sub-liquidus immiscibility of glasses are presented. Measurements were performed on the neutron small-angle scattering spectrometer of the Institut Laue-Langevin (Grenoble, France). The glass studied was 0.88 (SiO₂), 0.12 (Na₂O) from SiO₂Na₂O system which presents a well-known miscibility gap already explored by small-angle X-ray scattering (SAXS) method. Absolute values of the neutron scattering cross section as a function of scattering vector were obtained for this glass quenched and heat treated at 560°C for various lengths of time. It is shown that the ANS method can be used to follow phase separation kinetics and the comparison with SAXS results can in principle be used to separate the effects of density and concentration fluctuations in this system.     

Raman study of the structure of glasses along the join SiO2GeO2

In order to better understand the distribution of tetrahedra in multicomponent tetrahedral network structures of melts and glasses, we have investigated the Raman spectra of binary SiO₂GeO₂ glasses. We compare the Raman spectral features of the end-member glasses and discuss their vibrational origins. The mixing of GeO₂ and SiO₂ melts results in a continuous random network structure of TO₄ tetrahedra (T  Si, Ge) in the glass. Raman bands corresponding to the asymmetric stretch (v_as) of oxygen in GeOGe, SiOSi and SiOGe bonds are observed in the glasses having intermediate compositions along the SiO₂GeO₂ join. The presence of three distinct v_as (TOT) bands in the spectrum of a glass having Si/Ge one reveals that a considerable degree of SiGe disorder exists in the glass. The presence of a single symmetric oxygen stretching band in the spectra of binary SiO₂GeO₂ glasses indicates that the symmetric stretch modes (v_s) of oxygen in SiOSi, SiOGe and GeOGe bonds are strongly coupled. An observed decrease in the halfwidth of the v_s (TOT) band in the spectra of SiO₂GeO₂ glasses with increasing concentration of GeO₂ may be attributed to a decrease in the average TOT bond angle and a predominance of six-membered ring structures. Results of the present study support the assignment of the bands in the 900–1200 cm^?1 region of the alumino-silicate glasses, spectra to the v_as(AlOSi) and v_as(SiOSi) modes. In contrast to the alumino-silicate glasses, however, the SiO₂GeO₂ glasses have a much higher degree of disorder of the network-forming cations.     

Optical absorption of cobalt (II) in binary thallium borate glasses

The optical absorption spectra of cobalt (II) in Tl₂OB₂O₃ glasses have been studied and compared with those in binary alkali borate glasses. In thallium borate glasses cobalt (II) may be present in octahedral and/or in tetrahedral symmetry depending upon the composition of the glass. In low thallium borate glasses cobalt (II) is octahedral while the concentration of tetrahedral cobalt (II) increases with increasing Tl₂O content of the glass; the formation of tetrahedral cobalt (II) becomes noticeable when the concentration of Tl₂O reaches above the critical concentration of about 19 mol %. The ligand field parameters: 10Dq and B have been calculated from the absorption spectra of cobalt (II) in different glasses and it has been found that the Racah parameter, B, is more in Tl₂OB₂O₃ glasses than those in Na₂OB₂O₃ or K₂OB₂O₃ glasses of corresponding molar composition. This indicates that the donor capacity of the BO₄ group in thallium borate glasses is lower than that in alkali borate glasses; this is consistent with the NMR results in Tl₂OB₂O₃ glasses containing less than 20 mol % Tl₂O where three BO₄ groups have been found to form with each Tl₂O unit added.     

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.     

DC conductivity of ZnOV2O5 glasses

This work presents for the first time results regarding the DC conductivity of glasses belonging to ZnOV₂O₅ system. It is shown that the conduction can be described by a small polaron hopping model. The high temperature activation energy and conductivities are close to the values determined for V₂O₅P₂O₅ glasses of similar composition. The analysis of the pre-exponential factor shows strong evidence for a non-adiabatic conduction regime.This fact agrees with the conclusion drawn for the majority of vanadate glasses. The strong variation of α suggests the presence of fluctuations in the V⁵⁺ surroundings.     

Brillouin scattering measurements of attenuation and velocity of hypersounds in SiO2B2O3 glasses

Measurements of hypersound wave velocity and attenuation (20–30 GHz) were made at room temperature by Brillouin scattering in SiO₂O₂O₃ glasses. The attenuation shows a maximum with composition. An explanation of this maximum is given in relation to the glass structure. It is thought that this maximum may be due to a coupling effect of hypersounds with structural relaxational process involving SiSi and SiOB bonds.     

Electrical transport in n-type semiconducting Ge120BixSe70−xTe10 glasses

Resistivity and thermoelectric power were measured as a function of temperature and composition for Ge₂₀Bi_xSe_70?xTe₁₀ glasses (x = 0–11). The results were compared with the case of of Ge₂₀Bi_xSe_80?x glasses to see on the electrical properties the influence of the substitution of Te for a part of Se. The glasses show n-type conduction for x ? 9, which was not affected by the substitution of Te. The resistivity was about three orders of magnitude lower for the glasses with x < 10, and remained almost the same for x ? 10, compared with the glasses not containing Te. From the composition dependence of the calculated concentration of covalent bonds in the glasses, it was proposed that the appearance of n-type conduction was closely related to the formation of a sufficient number of BiSe bonds and the disappearance of the bonds between two chalcogen atoms such as TeSe or SeSe bonds, and that the remarkably low resistivity in the present glasses with x < 10 was likely to be attributed to the formation of TeSe bonds.     

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.     

Determination of ionic distributions of three sorts of oxygens in a few binary silicate glasses from molar refractivity

Ionic distributions of three sorts of oxygens in glasses in the systems Na₂OSiO₂K₂OSiO₂ and PbOSiO₂ were determined from molar refractivity. The distribution of these oxygen ions in PbOSiO₂ glasses was compared with that determined by the XPS method and with the theoretical calculation based on the athermal mixture model. The present result showed good agreement with that by the XPS method when the PbO content was 70 mol % or over, and showed a discrepancy when the PbO content was less than 70 mol %. It was indicated that a theoretical treatment based on a higher approximation that the athermal mixture model is required in order to enable the comparison with experiments for silica contents higher than 50 mol %.     

Sensitivity of the photo-darkening effect in CuAsSe glasses

When CuAsSe glasses are irradiated, they exhibit higher concentrations of darkening than AsSe glasses. Since darkening depends on the composition, the darkening centers in CuAsSe glasses to be of the same kind as those in AsSe glasses, i.e. arsenic clusters. Concerning the kinetics of erasing, it was found that the activation energy and the rate constant of erasing in CuAsSe are almost equal to those in AsSe glasses, but for the kinetics of darkening, it was found that the activation energy of darkening is equal to that of AsSe but α₀, which is proportional to the number of latent darkening centers, and the darkening rate constant k₁ are about twice as high as the corresponding constants of AsSe glasses. This may be the reason for the greater darkening in CuAsSe glasses. The high value of α₀ was attributed to the generation of more AsAs bonds on the addition of Cu to the AsSe glass network. The high value of k₁ was attributed to the increase in efficiency of photo-decomposition because of the many impurity levels in the band gap and also because of the narrow optical energy gap in the CuAsSe glasses.     

Microheterogeneities in infrared optical selenide glasses

Flocculent inhomogeneities in vitreous Ge₂Se₃ were identified as being SiO₂. The origin of these particles was found in the walls of the vitreous silica tubes in which the glass was prepared. By etching or thermal treatment of the tubes prior to their use the concentration of the microheterogeneities in the selenide glass can be considerably reduced. This is also valid for the preparation of glasses of the system GeAsSe and GeSbSe.     

Pressure effects on electrical conduction in glasses

Electrical conduction in various inorganic glasses was studied as a function of hydrostatic pressure up to 2000 atm and phenomenologically classified into electronic, ionic and mixed types. In electronically conducting glasses such as AsSe chalcogenide glasses and Fe₂O₃P₂O₅ glass, the conduction is enhanced by application of pressure. On the other hand in ionically conducting glass such as Na₂OB₂O₃ glass, the conduction is suppressed through the concept of an activation volume. The compatibility of electronic and ionic conduction processes in glasses such as Ag-doped AsSe glasses and Bi₂O₃B₂O₃ glass, which have more complex conduction processes, was discussed from these aspects.     

X-ray diffraction studies of glasses in the systems Na2OMeOSiO2 (MeMg,Zn, Ca,Ba)

X-ray diffraction studies of glasses in the following ternary systems have been made: Na₂OMgOSiO₂, Na₂OZnOSiO₂, Na₂OCaOSiO₂ and Na₂OBaOSiO₂. The following heavy atom substitutions have been used: Ag for Na and Ge for Si. The changes in the electron radial distribution curves resulting from AgNa replacement can be explained as amplifications of relatively well-defined NaSi distances, which are nearly the same in all the glasses investigated. The GeSi substitution causes changes which can be explained on the basis of isostructural GeSi substitutions.     

The short-range structure of alkali disilicate glasses by pulsed neutron total scattering

Time-of-flight total neutron scattering experiments using pulsed neutrons with short wavelength produced by an electron linear accelerator have been carried out to measure the structure factors of SiO₂ and M₂O · 2 SiO₂ (M = Li, Na and Li_0.63Na_0.37) glasses over a wide range of the scattering vector up to Q (=4π sin θ/λ) ～480 nm^?1. The Placzek correction has been considered up to the second order in the energy transfer. The Fourier transform of the structure factors yield the pair distribution functions highly resolved in real space, from which the stretching of the SiO and OO atomic distances and the number of bridging and non-bridging oxygen atoms in the alkali disilicate glass have been obtained.     

Electronic structure and properties of oxide glasses (II) Basicity measured by copper(II) ion probe in Na2OP2O5, K2OB2O3 and K2SO4ZnSO4 glasses

The correlation between the basicity of oxygens measured by the Cu(II) ion probe and the non-bonding electron density on oxygens in alkali borate glasses was considered. The basicity was measured for K₂OB₂O₃, Na₂OP₂O₅ and K₂SO₄ZnSO₄ glasses and categorized into two types, δ and π, according to the symmetry property of the bonding between a Cu(II) ion and oxygen. The π basicity for borate and phosphate glasses showed an abrupt increase in the vicinity of 17 and 50 mol% alkali oxide, respectively. The values of π-type basicity varied with the composition of glass, being larger in the order: sulfate < phosphate ? borate, whereas δ basicity was constant irrespective of the glass composition. Such a change of the basicity with the composition of glass was interpreted in terms of behavior of non-bonding levels of the ligand oxygens in a glass network.     

Structural investigation of amorphous FeZr,CoZr and NiZr alloys with low zirconium concentration

A structural investigation has been made of alloy glasses a low concentration of zirconium: compositions M_100?xZr_x with M = Fe, Co and Ni, and x = 9 at.% using X-ray diffraction. The characteristic second peak splitting in the radial distribution function is found for all samples presently investigated. The partial radial distribution functions of amorphous FeZr and CoZr alloys were derived from the measured total distribution function data by applying the concentration method with the anomalous scattering technique. The amplitude in the oscillation of the radial distribution function for M-M and M-Zr pairs is more enhanced in comparison with that of glasses with high Zr content, x = 40–45 at.%. The estimated coordination number of nearest neighbor Fe atoms (11.6 ± 0.5) for iron in the Fe₈₄Zr₁₆ glass is larger than that (10.7 ± 0.5) found in the Fe₈₃B₁₇ glass. This is consistent with the measurements of magnetic properties of these glasses with low zirconium concentration. The possible structural features of intertransition metal alloy glasses with low zirconium concentration is also discussed based on the present experimental data.     

Radiation effects in ZrF4 based glasses: I. Electron spin resonance

Binary ZrF₄BaF₂, HfF₄BaF₂, and multicomponent ZrF₄ based glasses have been studied by electron spin resonance spectroscopy after liquid-nitrogen-temperature X-irradiations and room-temperature γ-ray irradiations. Polycrystalline BaF₂, ZrF₄ and HfF₄ were investigated in the same manner for comparison purposes. Isochronal anneal experiments have distinguished several resonances in the glasses which are characterized as due to F₂^? molecular ions, F⁰ interstitial atoms and Zr³⁺ and Hf³⁺ ions. Two more signals are tentatively assigned as due to a hole trapped on several fluorine ions and a hole trapped on an oxygen impurity. In lead-containing glasses the formation of Zr³⁺ is strongly inhibited, presumably due to the competitive formation of Pb⁺ ions. However, the radiation production of Pb³⁺ ions was independently observed, thus suggesting that the Pb²⁺ ions may serve as traps for charge carriers of either sign. No defects were detected which could be explicitly associated with other cationic constituents, such as La³⁺, Al³⁺, or Li⁺.     

Some features of EPR and optical spectra of vanadium in aluminophosphate glasses

The EPR and optical spectra of vanadium in glasses of ternary Al₂O₃P₂O₅SiO₂ and Al₂O₃P₂O₅B₂O₃ systems have been measured. The results were compared with earlier data for vanadium in binary phosphate, aluminophosphate and silicaphosphate glasses and with results of de-Biasi for V⁴⁺ in crystalline powder α-crystobalite AlPO₄. The superpositions of two hyperfine spectra (ASB-I and ASB-II) were found for many glasses of ternary systems. Both spectra can be attributed to VO²⁺ ions. The intensity ratio of the ASB-II spectrum to ASB-I depends on glass composition but is great (> 7) for all the glasses. Only the ASB-II spectrum was observed in glasses with low concentration of Al₂O₃. The spectral parameters of ASB-II spectrum are g_| = 1.916–1.921; g_⊥ 1.980–1.988; A_| = (188?190) × 10^?4cm^?1 and A_⊥ = (74–77) × 10^?4cm^?1. Three intense bands at 370, 455 and 700 ans 720 nm observed in these glasses can be attributed to V³⁺ ions. The excellent agreement of the parameters of the EPR spectrum of V⁴⁺ ions in crystalline α-crystobalite AIPO₄ and ASB-II spectra in the glasses under study suggest the identical electron structure of the paramagnetic species. This species is believed to be characterized by optical bands at 680 and 790 nm which have been observed by de Biasi. The orbital mixing coefficients indicate strong tetragonal distortion of vanadyl complexes responsible for the ASB-II spectrum. It is assumed that VO²⁺ ions responsible for this spectrum act as modifiers fitting into the relatively small holes of the three-dimensional networks of phosphate glasses containing no cations of large radii. The microscopic basicity of oxygens in such holes must be about 0.48.     

Protonic conduction in alkaline earth metaphosphate glasses containing water

D.c. electrical conductivity data were obtained for M O·P₂O₅ glasses (M = Be, Mg, Ca, Sr, Ba) containing small amounts of water. The results suggest that the mobility of protons in the glasses increases with decreasing OH bonding strength. The relation between the proton concentration and the conductivity or the apparent activation energy was studied for calcium metaphosphate glasses containing various amounts of water. The conductivity was found to be proportional to the square of the proton concentration; the apparent activation energy decreased linearly with increasing logarithm of proton concentration.     

X-ray diffraction study of Na2OGeO2 melts

The structure of Na₂OGeO₂ melts in the temperature range from 1100 to 1150°C has been investigated with the high temperature X-ray diffraction technique. Comparing the radial distribution functions obtained for the melts with those for the corresponding glasses, the first peak due to the GeO interatomic distance is invariant upon melting, although it becomes broader due to thermal vibration. The second peak for the GeGe interatomic distance for melts shifts toward the large distance, which is explained by broadening of the GeOGe bond angle, not by the thermal expansion of the GeOGe bond. The composition dependences of GeO distances and coordination numbers of the Ge⁴⁺ ion of the melts are found to be almost the same as the corresponding glasses, indicating that even in melts at such high temperatures 6-fold coordinated Ge⁴⁺ ions are present and their content changes with the Na₂O content as in the case of the corresponding glasses.