Structural properties of Cr2O3–Fe2O3–P2O5 glasses,Part I

The structural properties of xCr₂O₃–(40 − x)Fe₂O₃–60P₂O₅, 0 ⩽ x ⩽ 10 (mol%) glasses have been investigated by Raman and Mössbauer spectroscopies, X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The Raman spectra show that the addition of up to 5.3 mol% Cr₂O₃ does not produce any changes in the glass structure, which consists predominantly of pyrophosphate, Q¹, units. This is in accordance with O/P ≈ 3.5 for these glasses. The increase in glass density and T_g that occurs with increasing Cr₂O₃ suggests the strengthening of glass network. The Mössbauer spectra indicate that the Fe²⁺/Fe_tot ratio increases from 0.13 to 0.28 with increasing Cr₂O₃ content up to 5.3 mol%, which can be related to an increase in the melting temperature from 1423 to 1473 K. After annealing, the 10Cr₂O₃–30Fe₂O₃–60P₂O₅ (mol%) sample was partially crystallized and contained crystalline β-CrPO₄ and Fe₃(P₂O₇)₂. The SEM and AFM micrographs of the partially crystallized sample revealed randomly distributed crystals embedded in a homogeneous glass matrix. EDS analysis indicated that the glass matrix was rich in Fe₂O₃ (39.6 mol%) and P₂O₅ (54.9 mol%), but contained only 5.5 mol% of Cr₂O₃. These results suggest that the maximum solubility of chromium in these iron phosphate melts is 5.5 mol% Cr₂O₃.     

27Al NMR structural study on aluminum coordination state in bismuth doped silica glass

The aluminum coordination state in bismuth doped silica glass, which has new broad infrared emission at 1.3 μm regions, was investigated by using ²⁷Al NMR, and it is demonstrated that 6-fold coordinated aluminum ions with corundum structure are dominant in bismuth doped silica glass until Bi₂O₃ concentrations of 1.0 mol% with Al₂O₃. The aluminum ion efficiently affects the creation of a Bi luminescent center at an intensity of Bi₂O₃ (1.0 mol%)–Al₂O₃ (2.3 mol%)–SiO₂ (96.7 mol%); the sample is three orders of magnitude larger than the Bi₂O₃ (1.0 mol%)–SiO₂ (99.0 mol%) sample. Aluminum ions with corundum structure in silica glass have a very important role for the configuration of peculiar Bi luminescent centers.     

Influence of europium ions on structure and crystallization properties of bismuth borate glasses and glass ceramics

Glasses of the xEu₂O₃ · (100?x)[2Bi₂O₃ · B₂O₃] system with 0 ? x ? 25 mol% have been characterized by X-ray diffraction and FTIR spectroscopy measurements. Melting at 1100 °C and the rapid cooling at room temperature permitted us to obtain glass samples. In order to improve the local order and to develop crystalline phases, the glass samples were kept at 625 °C for 24 h. After heat treatment two crystalline phases were put into evidence. One of the crystalline phases was observed for the host glass matrix, the x = 0 mol% sample, and belongs to the cubic system. The second one was observed for the x = 25 mol% sample and was find to be orthorhombic with two unit cell parameters very close to each other. For the samples with 0 < x < 25 mol% there is a mixture of the two mentioned phases. FTIR spectroscopy data suggest that both Bi₂O₃ and B₂O₃ play the glass network former role while the europium ions play the network modifier role in the studied glasses.     

Dissolution behavior of ZnO–P2O5 glasses in water

Bulk binary ZnO–P₂O₅ glasses with 50–70 mol% ZnO were immersed in distilled water at 30–90 °C for up to 72 h. The immersed samples were characterized by weight loss, the change in solution pH, X-ray diffraction (XRD) analysis, scanning electron microscopy and Raman spectroscopy. Weight loss decreased with ZnO concentration for all immersion temperatures. Dissolution behavior was classified into two types in terms of weight loss and macroscopic appearance. Type I was primarily recognized in 50–60 mol% ZnO glasses. In type I, the weight loss for 72 h was relatively large (>1.0 × 10⁻⁷ kg mm⁻², >10% of initial sample weight). Raman spectra of the type I glasses indicated that the depolymerization of phosphate glass network occurred during the dissolution process. Crystalline Zn₂P₂O₇ · 3H₂O was precipitated in the water solution after immersion. Type II dissolution behavior was recognized in the 65 and 70 mol% ZnO glasses except for the 65ZnO–35P₂O₅ glass immersed at 90 °C. In the type II behavior, the weight loss for 72 h was relatively-small (<1.0 × 10⁻⁸ kg mm⁻², <1% of initial sample weight). The microstructure of the type II glass indicated selective dissolution. The dissolution process of the type II glass is discussed.     

The effects of ZnCl2 and ErCl3 on the vibrational spectra and structure of tellurite glasses

A series of zinc tellurite glasses, containing up to 40 mol% ZnCl₂ and doped with 1–10 mol% ErCl₃, was prepared by melting and casting and their structure was analyzed by polarized Raman and variable incidence infrared reflection spectroscopies. Kramers–Kronig analysis of the infrared reflectivity led to the identification of the vibrational mode components. The Raman spectra are dominated by an intense, depolarized boson peak at ∼45 cm⁻¹ and a high frequency, polarized peak at ∼767 cm⁻¹. The introduction of ZnCl₂ and ErCl₃ modifiers led to a blue shift of the high frequency peak, while the intensity of the boson peak was found to increase continuously with the Er³⁺ content. It is shown that the erbium and zinc compounds both break TeOTe bonds, introducing non-bridging chlorine species, connected mostly to the zinc atoms.     

EPR and magnetic susceptibility studies of B2O3–Bi2O3–Gd2O3 glasses

Glasses of the xGd₂O₃ · (100 − x)[B₂O₃ · Bi₂O₃] system with 0.5 ⩽ x ⩽ 10 mol% were studied by electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. Data obtained show that for low gadolinium oxide contents of the samples (x ⩽ 3 mol%) the Gd³⁺ ions are randomly distributed in the host glass matrix and are present as isolated and dipole–dipole coupled species. For higher gadolinium oxide contents of the samples (x > 3 mol%) the Gd³⁺ ions appear as both isolated and antiferromagnetically coupled species. The EPR spectra of the glasses reveal resonance sites with an unexpected high crystalline field in addition to the ‘U’ spectrum, typical for Gd³⁺ ions in disordered systems. This absorption line is due to Gd³⁺ ions that replace Bi³⁺ ions from the host glass matrix and could play the network unconventional former role in the studied glasses.     

Efficient 1.53 μm erbium light emission in heavily Er-doped titania-modified aluminium tellurite glasses

Ti–Al co-doped erbium tellurite glasses have been obtained by melting mixed Er₂O₃, TiO₂ and TeO₂ batches in Al₂O₃ crucibles. By crucible dissolution Al₂O₃ amounts from 11.5 to 18.6 mol% were introduced in the synthesized glasses. Differential thermal analysis of glasses points to a strong dependence of glass transition temperature T_g with the substitution extent of TeO₂ by the doping oxides. No crystallization features are observed up to 450 °C. The spectral features and decay kinetics of the infrared photoluminescence of erbium demonstrate the possibility to achieve more than 50% of quantum yield of light-emission at Er³⁺ concentrations as large as 10²¹ cm⁻³, with about 2 ms of lifetime, 8 × 10⁻²¹ cm² of stimulated emission cross section, and no saturation at pump power densities higher than 10 kW cm⁻². The study of the kinetics of Er–Er energy transfer suggests to ascribe these features to a particularly homogeneous dispersion of Er³⁺ ions in the modified tellurite network. Raman scattering measurements of the spectral distribution of vibrational modes evidence that the introduction of doping oxides leads to an increase of structural disorder without crystallization effects.     

Effect of B2O3 addition on the thermal properties and density of barium phosphate glasses

Variations in glass transition temperature, onset of crystallization, thermal expansion coefficient, density and molar volume with B₂O₃ concentration were studied in a series of xB₂O₃–(100 − x)Ba(PO₃)₂ glasses with 0–10 mol% B₂O₃. DTA analysis and isothermal treatments for powdered glass samples reveal that ⩾7.5 mol% B₂O₃ addition suppresses surface crystallization during softening process. Raman spectroscopy suggests that the properties are related to the glass structure consisting of PO₄ Q² units with diborate and PO₄–BO₄ groups.     

FT-IR and Raman study of silver lead borate-based glasses

Glasses from the xMnO · (100−x)[3B₂O₃ · 0.9PbO · 0.1Ag₂O] system with 0 ⩽ x ⩽ 20 mol% have been prepared and studied by means of FT-IR absorption and Raman scattering. We interpreted the spectroscopic data in conjunction with the structural information obtained by X-ray diffraction and scanning electron microscopy (SEM). The X-ray patterns have showed homogenous glasses over the entire compositional range while the SEM pictures have detected metallic silver or Ag₂O clusters dispersed in the glass network. Acting as complementary spectroscopic techniques, both types of measurements, FT-IR and Raman, revealed that the network structure of the studied glasses is mainly based on BO₃ and BO₄ units placed in different structural groups, the BO₃ units being dominant. The influence of manganese-ion content (x), on the N_BO4/N_BO3 ratio evolution was investigated.     

Aluminoborate and aluminoborosilicate glasses with high chemical durability and the effect of P2O5 additions on the properties

Several series of SrTiO₃–aluminoborate and SrTiO₃–aluminoborosilicate glasses were prepared, which exhibited low corrosion rates in water at 90 °C. The additions of up to 9 mol% P₂O₅ to these glasses were found to significantly improve the chemical durability. The weight loss rate of a glass with the nominal composition (mol%) 15SrO–15TiO₂–23.3Al₂O₃–46.7B₂O₃ decreased by over two orders of magnitude with the additions of up to 9 mol% P₂O₅. In contrast, P₂O₅-additions increased the dissolution rate of the silicate analog of the initial borate glass, 15SrO–15TiO₂–23Al₂O₃–47SiO₂. The positive effect of small P₂O₅ additions on the chemical durability of the aluminoborate glasses may be attributed to the replacement of BO₃ units by BO₄ units in the glass network, as indicated by infrared and Raman spectra.     

Optical phonons and Raman scattering in ternary II–VI spheroidal nanocrystals embedded in a glass matrix

Theoretical and experimental studies of the spatial phonon confinement in ternary CdS_xSe_1−x nanocrystals embedded in a glass matrix formed by the composites (40)SiO₂₋(30)Na₂CO₃–(29)B₂O₃–(1)Al₂O₃ (mol%) + [(2)CdO + (2)S + (2)Se] (wt%) were carried out. From the analysis of the surface phonon modes, the theoretical procedure has allowed the determination of the geometrical characteristics of the nanocrystals. The calculated frequencies were compared with the experimental values obtained from the Raman spectra of CdS_xSe_1−x nanocrystals grown under different thermal treatments. A good correlation between the experimental and calculated CdS-like and CdSe-like surface optical modes was observed. The Raman selection rules and their connection with the nature of the surface optical phonons is discussed in order to use Raman spectroscopy as a probe to determine the composition x and the geometrical shape of the semiconductor nanocrystals.     

Structure–property correlations in lead borate and borosilicate glasses doped with aluminum oxide

Glass samples from four systems: xPbO–(100?x)B₂O₃ (x = 30, 40, 50 and 60 mol%), 50PbO–yAl₂O₃–(50?y)B₂O₃ (y = 2, 4, 6, 8 mol%), 50PbO–ySiO₂–(50?y)B₂O₃ (y = 5, 10, 20, 30 mol%) and 50PbO–5SiO₂–yAl₂O₃–(45?y)B₂O₃ (y = 2, 4, 6, 8 mol%) were prepared by a melt-quench technique. Characterization of these systems was carried out using density measurements, UV–visible spectroscopy, differential scanning calorimetry (DSC), and ¹¹B and ²⁷Al magic-angle spinning (MAS) solid-state nuclear magnetic resonance (NMR). Our studies reveal an increase in glass density with increasing lead(II) oxide concentration in pure lead borates and also with addition of silica into 50PbO–50B₂O₃ glass. ¹¹B MAS NMR measurements determine that the fraction of tetrahedral borons (N₄) reaches a maximum for the glass containing 50 mol% of PbO in the PbO–B₂O₃ glass series and that N₄ is sharply reduced upon adding small amounts of Al₂O₃ into lead borate and lead borosilicate systems. ²⁷Al MAS NMR experiments performed on glasses doped with aluminum oxide show that the Al³⁺ are tetra-, penta- and hexa-coordinated with oxygen, even without any excess concentration of Al³⁺ over charge-balancing Pb²⁺ cations. ^[5]Al and ^[6]Al concentrations are found to have unusually high values of up to 30%. The results of UV–visible absorption spectroscopy, DSC and density measurements support the conclusions drawn from the NMR studies, providing a consistent picture of structure–property relations in these glass systems.     

Short-range structure and in vitro behavior of ZnO–CaO–P2O5 bioglasses

Ternary zinc–calcium-phosphate glasses prepared by classical melting method were characterized through X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) along with energy dispersive X-ray analysis (EDAX), Fourier Transform InfraRed (FTIR) and Raman spectroscopy. The study of these glasses was done in order to supply information regarding their structural particularities since the zinc role in biological environment, especially in the bone, is still under debate.XRD analysis confirmed the vitreous character of the as-prepared samples, while SEM and EDAX measurements indicated the presence of some non-homogeneous domains on their surfaces with approximately similar elemental composition. According to FTIR and Raman spectroscopy, the local structure of glasses up to 10 mol% ZnO is mainly built by Q² tetrahedrons connected by P–O–P linkages. For 50 mol% ZnO, the modifier role of zinc ions is strongly reflected on the local structure dominated in this case by Q¹ pyrophosphate units.The surface reactivity of the samples has been analyzed in vitro by immersion in simulated body fluid (SBF) at 37 °C. XRD, SEM–EDAX, FTIR and Raman methods were employed to characterize the structural changes that occurred on the surface of ZnO–CaO–P₂O₅ samples reacting with SBF. The X-ray diffraction patterns demonstrated the formation of a hydroxyapatite layer on the samples surface while the other used methods didn't reveal concisely that phenomenon. Based on X-ray measurements, the influence of zinc concentration on the hydroxyapatite layer development was followed.     

Thermal and optical properties of TeO2–BaO–SrO–Nb2O5 based glasses: New broadband Raman gain media

We systematically added WO₃ (up to 10 mol%) and P₂O₅ (up to 16 mol%) in TeO₂–BaO–SrO–Nb₂O₅ (TBSN) glass system and studied thermal and optical properties of the resultant glasses. The dependences of the additive concentration on glass transition (T_g) and crystallization (T_x) temperatures are presented. The TBSN glass added with ⩾4 mol% WO₃ and P₂O₅ showed high stability against crystallization. The changes in optical band gap energy due to WO₃ and P₂O₅ addition was studied using UV–VIS–NIR absorption spectrometry. The WO₃ addition shifted the optical band gap to longer wavelengths, whereas P₂O₅ addition shifted that to shorter wavelengths. Effects of the WO₃ and P₂O₅ addition on the Raman spectra of TBSN glass are clarified. New Raman bands due to WO₄ and PO₄ tetrahedra formed in the resultant glasses broadened their Raman spectra. Present glasses are characterized by higher thermal stability and wider Raman spectra, therefore, they are promising candidates for fiber Raman amplifiers in photonics systems.     

Electronic conductivity in zinc iron phosphate glasses

The electrical properties of (40−x)ZnO–xFe₂O₃–60P₂O₅ (x = 10, 20, 30 mol%) glasses were measured by impedance spectroscopy in the frequency from 0.01 Hz to 4 MHz and the temperature range from 303 to 473 K. It was shown that the dc conductivity strongly depends on the Fe₂O₃ content and Fe(II)/Fe_tot ratio. The increase in dc conductivity for these glasses is attributed to the increase in Fe₂O₃ content from 10 to 30 mol%. With increasing Fe(II) ion content from 6% to 17% the dc conductivity increases. This indicated that the conductivity arises mainly from polaron hopping between Fe(II) and Fe(III) ions suggesting an electron conduction in these glasses. By applying scaling on conductivity data measured at different temperatures, single master curve was obtained for each glass. On the other hand, deviation from the master curve at high frequencies was observed for glasses with different compositions. This deviation originates from a various mobility of charge carriers in different glass structures. Raman spectra showed the change of structure, from metaphosphate to pyrophosphate, with increasing Fe₂O₃ content from 10 to 30 mol%.     

Structure and properties of Sb2O3-containing zinc borophosphate glasses

ZnO–B₂O₃–P₂O₅ glasses formulated with Sb₂O₃ were investigated in the series 50ZnO–10B₂O₃–40P₂O₅ + xSb₂O₃ (x = 0–70 mol%). With increasing Sb₂O₃ content, the values of glass transition temperature decrease from 492 °C down to 394 °C. The dissolution rate of the glasses reveals a maximum for the glass with x = 15 mol% Sb₂O₃. Raman spectra with increasing Sb₂O₃ content reflect the depolymerisation of phosphate chains. Antimony at low Sb₂O₃ content forms individual SbO₃ pyramids manifested in the Raman spectra by a broad vibrational band at ∼520–690 cm⁻¹. In the glasses with a higher Sb₂O₃ content SbO₃ units link into chains and clusters with Sb–O–Sb bridges manifested in the Raman spectra by a strong broad band at 380–520 cm⁻¹. The ³¹P MAS NMR spectra with increasing Sb₂O₃ content reflect the depolymerisation of phosphate chains at low Sb₂O₃ content and only small changes in the PO₄ coordination at a high Sb₂O₃ content. ¹¹B MAS NMR spectra reveal a steady transformation of B(OP)₄ units into B(OP)_4−x(OSb)_x units, accompanied by the transformation of BO₄ into BO₃ units with increasing Sb₂O₃ content.     

Low-frequency Raman scattering and small-angle X-ray scattering of glasses inclined to phase decomposition

Low-frequency (<1000 cm⁻¹) Raman scattering of lithium aluminosilicate (12Li₂O : 15Al₂O₃ : 73SiO₂ with 4 mol% TiO2) glasses with addition of titanium dioxide has been studied. With a heat treatment at temperatures 660°C, 700°C, 720°C and 820°C and for various times and sequences of temperature, our samples decompose into nanometer sized dispersed aluminotitanate particles. In Raman spectra of these glasses an evolution of a boson peak was observed. The width of the relatively broad boson band decreases as does the frequency of the band. From small-angle X-ray scattering data we conclude that the boson peak is connected with elastic vibrations of amorphous or crystalline regions of inhomogeneity with a dimension of ∼1.7 nm in initial glasses or larger depending on the heat treatment sequences.     

Raman spectroscopic study of some lead phosphate glasses with tungsten ions

The structure of xWO₃ · (100 − x)[2P₂O₅ · PbO] glass system with 0 ⩽ x ⩽ 50 mol% was investigated by Raman spectroscopy. The characteristic bands of these glasses due to the stretching and bending vibrations were identified and analyzed by the increasing of WO₃ content. This fact allowed us to identify the specific structural units which appear in these glasses and thus to point out the network modifier role of tungsten oxide for low concentrations and its former role at high concentrations.     

Crystal-field spectroscopy of Eu3+ doped silica glasses

Fourier transform absorption spectroscopy in the 500–6000 cm^? 1 and 9–300 K ranges is applied to monitor the effects produced by Eu³⁺ incorporation into sol–gel silica samples doped with concentration increasing from 0.001 to 10 mol%. The aim is to investigate the formation of aggregates by exploiting the Eu³⁺ crystal-field transitions. Complementary microreflectance and Raman spectra are also measured in the range of silica intrinsic vibrational modes to confirm the hypothesis of matrix modification induced by increasing doping levels. Evidences of clustering are found for high Eu³⁺ concentrations. Up to 3 mol% the crystal-field line intensities gradually increase and the OH^? content smoothly decreases. A further increase to 10 mol% causes drastic, remarkable changes, i.e. sharp crystal-field lines appear which narrow by lowering the temperature. Furthermore, the OH^? related bands are no longer detectable. For concentrations up to 3 mol% the aggregates are amorphous as the silica matrix, while for the Eu³⁺ 10 mol% sample they show a rather ordered structure.     

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.