Optical spectra of sodium phosphate glasses

The visible, infrared, and ultraviolet spectra of seven glasses in the Na₂OP₂O₅ binary system were obtained. Changes in spectra were related to structural changes occurring the glass. Dopant ions Co²⁺, Cu²⁺, and Pb²⁺ were used to infer structural changes occurring as the metaphosphate composition was crossed going from pyrophosphate compositions into ultraphosphate compositions. The presence of chemically bound water was found to cause the overall modifier-to-former ratio to remain constant for glasses containing greater than 65 mol.% P₂O₅.     

Structural characterization of phosphate glasses doped with silver

The present paper reports the influence of silver oxide addition on the local structure of 2P₂O₅ · CaO · 0.05ZnO glass matrix. The glass samples were investigated through several methods: X-ray powder diffraction (XRD), scanning electron microscopy (SEM), infrared absorption (FT-IR) and Raman scattering. The X-ray diffraction patterns confirm the vitreous character of these samples over the explored compositional range and the SEM pictures confirm this information. The phosphate structural units of the network former are assessed from FT-IR and Raman spectra as ultra-, meta-, pyro- and orthophosphate units. A slight structural depolymerization process of these phosphate-based glasses was evidenced for higher silver oxide content. In vitro behavior of the bulk glass sample with the highest silver oxide content was tested by immersion in simulated body fluid (SBF). X-ray diffraction and SEM measurements made on the SBF treated sample revealed growth of a crystalline phase on the surface sample.     

Electrical properties of phosphate glasses

The electrical properties of glasses in the Na₂OP₂O₅, Ag₂OP₂O₅ and (1?x)Na₂OxAg₂OP₂O₅ systems have been measured over a range of temperature and composition.The properties of the Na₂OP₂O₅ and Ag₂OP₂O₅ glasses have been compared within the phosphate system as well as with silicate glasses. The silver-containing glasses show higher conductivity and lower temperature coefficients when compared with the sodium-containing glasses. A maximum in the room temperature resistivity of the (1?x)Na₂O?xAg₂O?P₂O₅ system was found around the mole ratio of 0.16:0.84 Ag₂O:Na₂O, indicating a mixed-alkali effect. A similar effect was seen in the tan δ, but not in the T_g-against-composition plots. A linear relationship was noted for the tan δ-versus-log₁₀ (resistivity) plot, as has been seen in other glass-forming systems.     

Optical properties of zinc molybdenum phosphate glasses

Zinc molybdenum phosphate (ZnO–MoO₃–P₂O₅) glasses of different compositions were prepared and synthesized and some of their properties were studied. The optical band gaps have been deduced from spectral dependence curves. The infrared absorption spectra of these investigated glasses were found analogous to SrO–Fe₂O₃–P₂O₅. Annealing at different temperatures does not show a prominent change in absorption band positions. We correlate our findings with a possible structural explanation of these glasses.     

IR absorption spectra of lithium and silver vanadium–tellurite based glasses

The aim of the present paper is to give structural information in order to set a correlation between the electrical conductivity behavior and structures of lithium and silver vanadium–tellurite based glasses. We report our structural studies and compare the effect of the nature of the metallic cation on glasses of the form XM₂O · (1 − X)V₂O₅ · 2TeO₂ (where 0 ⩽ X < 1 and M = Li or Ag). Fourier transform infra-red (FTIR) spectra were recorded for all compositions and complementary differential scanning calorimetry (DSC) measurements and X-ray diffraction (XRD) measurements were also carried out. This paper should be considered as complementary to a previous article reporting the conductive behavior of theses glasses. In the latter we reported the obtained results on electrical conductivity studies. The results confirm the existence of a transition from a typically electronic (polaronic) conductive regimen when the molar fraction (X) of M₂O is equal to 0, to an ionic conductive regimen when X tends to 1. The evidence for the independent migration path for both electrons and ions was put into evidence by studying the electrical conductivity behavior in a complementary system of the form X M₂O · (1 − X)[0.5V₂O₅–0.5MoO₃] · 2TeO₂. In this system vanadium was partially replaced by molybdenum which acts as a ‘diluting’ agent of the active centers involved in the electronic transport.     

Dielectric properties and structural features of barium-iron phosphate glasses

The dielectric constant of barium-iron phosphate glasses with the general composition (40−x)BaO · xFe₂O₃ · (60−x)P₂O₅ has been investigated at two fixed frequencies (100 kHz and 9.0 GHz). The dielectric constant measured using microwave technique, and the ratio O/P of these glasses increase with increasing Fe₂O₃ content. The structure and valence states of the iron ions in these glasses were investigated using Mössbauer spectroscopy, infrared spectroscopy and differential thermal analysis. Both Fe(II) and Fe(III) ions present in these glasses in octahedral coordination act as permanent dipoles, and the increase of the iron concentration increase these permanent dipoles, contributing to the dielectric constant.     

Photoluminescent properties and Raman spectra of ZnO-based scintillating glasses

Glasses in SiO₂–ZnO–BaO system with the different ZnO/BaO ratio were studied. In some cases, BaF₂ was introduced to substitute for BaO on the equal base. Photoluminescent spectra showed that ZnO in glass matrices behaved somewhat differently from ZnO crystals. Especially, the introduction of fluorine ions led to dramatic shift of UV emission band of glasses closer to that of ZnO crystals. Raman spectral analysis provided consistent results. In particular, Raman bands in the high frequency region are sensitive to effects of different ZnO/BaO or BaF₂/BaO ratio on structure of glasses.     

Electrical properties of copper phosphate glasses II. Dielectric properties

The ac and dc electrical properties of the P₂O₅BaOCuO glass system have been measured.TSPC and TSDC experiments and dc conductivity as a function of time indicate the predominantly electronic character of these glasses. The conduction process can be basically explained by a polaron hopping model in an adiabatic regime. Conductivity values which depend on the glass microstructure and switching phenomena are observed. The filamentary-feature of this process suggests a Poole-Frenkel mechanism.A Debye dielectric relaxation non-simple process is deduced from the frequency and temperature dependence of loss tangent and dielectric constant. The activation energies agree with those determinated from dc measurements, suggesting a unique electronic hopping conduction mechanism in both regimes.The ac and dc electrical properties are strongly affected by the glass composition and essentially by the redox Cu⁺/Cu_t ratio.A conduction model accounting for ac and dc behaviour is finally proposed.     

Optical properties of fluorine-substituted zinc bismuth phosphate glasses

The effects of the substitution of fluoride ions for oxide ions on the thermal and optical properties of ternary ZnO-Bi₂O₃-P₂O₅ glass with low-P₂O₅ content (20-25 mol%) were investigated. Fluoride ions were introduced into the glass up to about 12 mol% as ZnF₂. Raman spectra indicated that fluoride ions were substituted for oxide ions connected with bismuth ions. Deformation and glass transition temperatures decreased monotonically with fluorine concentration. The absorption edge shifted toward higher energies with increasing fluorine concentration by about 0.3 eV for 12 mol% ZnF₂ substitution. The blue shift of the absorption edge is attributable to two effects. One was a blue shift of an absorption band which was observed as a peak at 4.7 eV in the reflection spectra and was attributed to the spin forbidden 6s-6p interband transition in Bi³⁺ ions. The blue shift originates from a change in electron-donating ability through anions as expected from electronegativity or optical basicity. Another is a disappearance of a shoulder at around 4.3 eV in the reflection spectra. The latter was the major reason for the large blue shift of the absorption edge energy, because the band relating to the 4.3 eV shoulder is close to the absorption edge.     

Structure of rare-earth phosphate glasses by X-ray and neutron diffraction

Previous diffraction studies of the structures of rare-earth phosphate glasses (R₂O₃)_x(P₂O₅)_1−x are extended to glasses with smaller R³⁺ ions with R = Sm, Gd, Dy, Er, Yb, Y for x = ∼0.25 and with R = Nd, Sm, Gd for x = ∼0.15. Parameters for the P–O, R–O and O–O first-neighbor peaks were obtained by Gaussian fitting. P–P and R–P distances were estimated from the positions of peak maxima. Effects of residual silica or alumina contents present as a result of glass processing were taken into account for selected samples. The P–O coordination number, N_PO, and the P–O, O–O, P–P distances are consistent with the presence of phosphate tetrahedra and are insensitive to the R species and the R₂O₃ content. Rare-earth coordination numbers, N_RO, decrease from ∼8 to ∼6.5 when x is increased from ∼0.15 to ∼0.25. N_OO and N_PP decrease with increasing R₂O₃ content indicating the network disintegration. The numbers N_RO of the metaphosphate glasses (x = ∼0.25) decreases from ∼7 to ∼6 when R is changed from La to Yb. This change is also indicated by the behavior of the R–O distances and by constant number densities of atoms. The decrease in N_RO with increasing R₂O₃ content is due to the reduction in the number of terminal O (O_T) available for coordination of the R³⁺ ions (six at metaphosphate composition). Especially for smaller R³⁺ ions sharing O_T between two R sites is not favored. The decrease by ∼0.04 nm of the prominent R–R first-neighbor distance with a change of R from La to Yb at the metaphosphate composition is indicated by a shift to higher magnitude of scattering vector of the shoulder occurring in front of the first main diffraction peak.     

Structure and properties of potassium niobato-borophosphate glasses

Bulk glasses of the series (1 ? x)[0.5K₂O–0.1B₂O₃–0.4P₂O₅]–xNb₂O₅ with x = 0–45.7 mol% Nb₂O₅ were prepared by slow cooling in air and investigated by Raman, ³¹P, and ¹¹B MAS NMR spectroscopy. The incorporation of Nb₂O₅ into the parent borophosphate glass results in a substantial increase in the glass transition temperature and chemical durability of glasses. Raman spectra showed that Nb atoms form distorted NbO₆ octahedra, which are isolated at low Nb₂O₅ content, whereas at higher Nb₂O₅ content they form clusters. ¹¹B NMR spectra of the glasses revealed the interaction between Nb₂O₅ and BO₄ tetrahedral units, which results in a partial transformation of tetrahedral BO₄ units to trigonal BO₃ units and the formation of mixed B(OP)_4?n(ONb)_n units.     

Structure and properties of lithium thio-boro-germanate glasses

Structural studies of the ternary xLi₂S + (1 − x)[0.5B₂S₃ + 0.5GeS₂] glasses using IR, Raman, and ¹¹B NMR show that the Li₂S is not shared proportionately between the GeS₂ and B₂S₃ sub-networks of the glass. The IR spectra indicate that the B₂S₃ glass network is under-doped in comparison to the corresponding composition in the xLi₂S + (1 − x)B₂S₃ binary system. Additionally, the Raman spectra show that the GeS₂ glass network is over-modified. Surprisingly, however, the ¹¹Boron static NMR gives evidence that ∼80% of the boron atoms are in tetrahedral coordinated. A super macro tetrahedron, B₁₀S₁₈⁻⁶ is proposed as one of the structures in these glasses in which can account for the apparent low fraction of Li₂S present in the B₂S₃ sub-network while at the same time enabling the high fraction of tetrahedral borons in the glass.     

Structure and properties of lanthanum galliogermanate glasses

Lanthanum galliogermanate glasses were prepared. Raman spectra, molar volumes, glass transition temperatures and activation energies for glass transition and crystallization were obtained. For glasses having the same La₂O₃/GeO₂ ratio, the molar volumes increase with the Ga₂O₃ content, and the glass transition temperatures, activation energies for glass transition and crystallization, increase initially then decrease as the ratio of Ga₂O₃/GeO₂ increases. For glasses having the same Ga₂O₃/GeO₂ ratio, the molar volumes increase with La₂O₃ content, and the glass transition temperatures increase as the ratio of La₂O₃/GeO₂ increases. The change of glass structure and its properties with composition is correlated with the concentration of lanthanum ion.     

The elastic properties of some phosphate/vanadate glasses

The elastic constants of 7 phosphate/vanadate glasses, containing TiO₂, Na₂O and a range of concentrations of CuO, have been measured from 4.2 to 300 K. The pressure variation of the elastic constants has also been measured and has been used to calculate the low temperature value of the Grüneisen parameter γ_O for these glasses. Analysis of the results and other data has been used to show how TiO₂, Na₂O and CuO may be incorporated in the structure of these P₂O₅/V₂O₅ glasses.     

The electron paramagnetic resonance and optical spectra of copper and vanadium in phosphate glasses

In the present work the results of the systematic study of the EPR spectra of Cu²⁺ and V⁴⁺ ions in binary phosphate glasses are discussed. A comparison of the behaviour of the EPR spectra of two kinds of ions in the same glassy matrix allows one to determine more accurately the location of each kind of ions in this matrix. This paper deals mainly with the phosphate glasses ROP₂O₅ containing divalent modificators (R = Ca, Sr, Ba, Mg, Zn, Pb). The optical spectra were recorded on a SP-8 spectrophotometer in the range 300–1000 nm. The EPR spectra were recorded at room temperature on the EPR-3 spectrometer made in the USSR and operating in the X-band.     

Structure and magnetic properties of lead vanadate glasses

X-ray photoelectron spectroscopy (XPS) has been used to obtain structural information on the xPbO · (1−x)V₂O₅ glass system where x=0.22, 0.35, 0.43, and 0.54. The binding energies from the Pb 4f_7/2 and Pb 4f_5/2 core levels decrease with increasing PbO content while the full-width at half-maximum of these peaks increase. The O 1s spectra show an asymmetry for samples having composition x<0.5, which results from oxygen atoms in the V–O–V configuration (bridging oxygens) and from oxygen atoms in the V–O–Pb and Pb–O–Pb configurations (non-bridging oxygens). The number of non-bridging oxygens was found to increase from 81% to 92% with increasing PbO content. For x=0.54, the O 1s spectrum was symmetric indicating that all three oxygen configurations have essentially the same binding energy. This behavior in addition to the decreasing binding energies of the Pb 4f levels with increasing PbO content suggest that the Pb–O bonds are becoming more covalent in nature and that eventually PbO changed its role from a glass modifier to a glass former for x>0.5. The asymmetric V 2p_3/2 peaks for the x<0.4 glasses indicate the presence of a small concentration of V⁴⁺ ions in addition to V⁵⁺ ions, while the symmetric V 2p_3/2 peaks for the more concentrated PbO vanadate glasses indicate only V⁵⁺ being present. The concentration of V⁴⁺ ions (0–4%) from the XPS data is consistent with determinations from magnetic susceptibility measurements on the same glass samples. In addition to the paramagnetic contribution (Curie–Weiss temperature-dependent behavior) from the V⁴⁺ ions, the susceptibility for these oxide glasses consisted of a positive, constant contribution arising from the temperature-independent paramagnetic V₂O₅ exceeding the diamagnetism from the core ions.     

Optical properties of bismuth in germanate,borax and phosphate glasses

Absorption, emission, excitation spectra and quantum efficiencies of luminescence of bismuth were obtained in germanate, borax and phosphate glasses. Decay times were measured for fluorescence of bismuth in germanate glass at room temperature and liquid air temperature. A non-exponential decay of fluorescence at room temperature is observed. A thermal equilibrium between the ³P₁ and ³P₀ states is discussed. The dependence of fluorescence intensity and decay times on temperature is presented. The amount of covalency between bismuth and glass matrix was calculated from the nephelauxetic effect.     

Optical properties of Nd3+ in lead phosphate glasses

Measurements of optical absorption and emission spectra of Nd³⁺ in lead phosphate glasses at 295 K are compared with results reported earlier for various metaphosphate glasses. The Judd-Ofelt intensity parameters for high-lead-content phosphate glasses are the smallest observed thus far for metaphosphate glasses with divalent network modifier cations.