FTIR and UV–VIS optical absorption spectra of gamma-irradiated MoO3-doped lead borate glasses

Structure and optical properties of MoO₃-doped lead borate glasses which contain high PbO content (60, 70 and 80%) have been studied using Fourier transform infrared (FTIR) and ultraviolet–visible (UV–VIS) spectroscopic tools. FTIR spectra reveal absorption bands which are characteristic for various structural units of borate network, mainly BO₃ triangles and BO₄ tetrahedra, in addition to the PbO_n (where n = 3 and/or 4) structural units. UV–VIS optical absorption spectra reveal broad intense charge transfer UV bands due to Pb^2 + ions in the range 320–385 nm. Within this range, molybdenum ions, preferably Mo^3 + and Mo^5 +, can interfere at about 360–385 nm. Additionally, molybdenum ions give a weak visible band at about 850–860 nm. The optical absorption spectra of the studied glasses show marked resistance to successive gamma irradiation up to 5 Mrad. This shielding behavior can be related to the present high content of the high atomic mass Pb^2 + ions. Changes in the atomic structure before and after gamma irradiation are described and explained.     

FTIR and UV–VIS spectroscopy investigations on the structure of the europium–lead–tellurate glasses

Glasses in the xEu₂O₃·(100-x)[4TeO₂·PbO₂] system where 0 ≤ x ≤ 50 mol% have been prepared using the melt quenching method. The influence of europium ions on the structure of lead–tellurate glasses has been investigated using density measurements, FTIR and UV–VIS spectroscopy. Structural changes produced by increasing the rare earth concentration were followed.The europium and lead ions show a preference towards [TeO₃] structural units causing a deformation of the TeOTe linkages. Structural changes inferred by analyzing the band shapes of IR spectra revealed that the increase of the Eu^+ 3 content causes the intercalation of [EuO_n] entities in the [TeO₄] chain network. The excess of oxygen can be supported into the glass network by the formation of [PbO_n] and [EuO_n] structural units.The UV–VIS spectroscopy data show that europium ions enter the glass matrix in the Eu²⁺ and Eu³⁺ valence states, the last being predominant in the studied glasses. The Pb^+ 2 ions produce strong absorption in the ultraviolet domain.     

Dielectric properties,conductivity, UV–visible and infrared spectroscopy of PbO P2O5 NaF glasses containing WO3

Homogeneous (50P₂O₅–(30 ? x)PbO–20NaF–xWO₃ where x = 0.0, 5, 10 and 15 mol%) glasses were synthesized using a melt-quenching method. The short range structures of the phosphate samples were examined by Fourier transform infrared spectroscopy. The infrared spectral studies have pointed out the existence of conventional PO₄, WO₄ and WO₆ structural units in the glass network, the number of WO₄ tetrahedra decreases as WO₃ concentration increases. The optical transmittance and reflectance spectrum of the glasses have been recorded in the wavelength range of 190–1100 nm. The values of the optical band gap E_op for all types of electronic transitions and refractive index have been determined and discussed. The real and imaginary parts ε₁ and ε₂ of the dielectric constant have been determined. The type of electronic transitions in the present glass system is indirectly allowed and the high values for the refractive index and dispersion are recorded due to the high polarizability of tungsten ions. The results of refractive indices as determined reveal the homogeneity of samples and were found to depend on the glass composition. The electrical properties of the glasses were investigated by ac conductivity from 0.12 to 100 kHz for temperatures ranging from room temperature to 600 K. The study of dielectric properties suggested increase in the insulating character of the glass system with increase in the content of WO₃. The ac conductivity in the high temperature region seems to be connected mainly with the polarons involved in the process of transfer from W⁴⁺ to W⁵⁺ ions.     

Structural modifications induced by addition of copper oxide to lead–phosphate glasses

xCuO(1-x)[P₂O₅·PbO] glass system with 0 ≤ x ≤ 50 mol% was prepared and investigated by means of EPR and IR spectroscopy in order to evidence the structural changes induced by different amounts of copper ions. EPR spectra analysis together with EPR parameters has indicated a distorted tetragonal symmetry – named tetrahedral local symmetry – for Cu^2 + ions in the studied glasses. A change in the shape of EPR spectra was also observed as for small CuO concentration (x < 20 mol%) these glasses present an asymmetrical line typical for isolated ions and for high CuO content this line is replaced by a symmetrical one characteristic of clustered ions through dipole–dipole interactions. IR spectra of the studied glasses put in evidence a strong depolymerization effect with a gradual increase of CuO. The shift of PO asymmetric stretching vibration band to lower wave number can be explained by the increase of PO₄ tetrahedra charge density leading a more ionic and less covalent bonding.     

Quantitative UV–VIS spectroscopic studies of photo-thermo-refractive glasses. I. Intrinsic,bromine-related,and impurity-related UV absorption in photo-thermo-refractive glass matrices

The paper opens up a series of papers on the origin and parameters of spectral features forming the absorption of photo-thermo-refractive (PTR) glasses in the UV. Problems to be cleared for gaining further insight into the spectroscopic manifestations of species responsible for the photo-induced processes in PTR glasses are discussed. The samples of bromine-containing and bromine-free PTR glass matrices are synthesized and their absorption spectra in the 28,500 to 50,000 cm^–1 region are recorded. The dispersion analysis of the spectra is conducted based on the convolution model for the complex dielectric function of glasses. The matrix electronic transitions that set the real part of the complex dielectric function and form the intrinsic absorption tail of the matrix are simulated with a series of effective oscillators. Spectral features forming the total absorption spectrum of PTR glass matrices in the 28,500 to 50,000 cm^–1 region are deconvoluted. These features are (i) the intrinsic absorption tail, (ii) for the bromine-containing matrix, the low-wavenumber wing of an envelope around ~ 51,400 cm^–1 covering the bromine-related spectral feature(s), (iii) Fe²⁺- and Fe³⁺-related impurity bands, and also (iv) a structureless absorption mostly due to the high-wavenumber wings of other impurity bands below 28,500 cm^–1.     

X-ray absorption near edge structure investigation of iron–sodium silicate glasses

X-ray absorption near edge structure spectroscopy has been used at the O K and Fe L_2,3 edges to investigate the electronic and atomic structure of (Fe₂O₃)_x(Na₂O)_0.30(SiO₂)_0.70 ? x (x < 0.2) obtained by melt-quench technique. The Fe L_2,3 edge spectra show that the Fe atoms are in octahedral coordination. The O K edge spectra reveal no change in coordination of Fe and increased degree of hybridization between O 2p and Fe 3d orbitals with iron doping. It is estimated that about 10% Fe²⁺ and 90% Fe³⁺ are in these glasses by peak fitting analysis of Fe L₃ edge. The ligand-field splitting of Fe 3d orbital is about 1.6 eV.     

Raman and infrared spectra of As2Sx chalcogenide glasses with x ⩽ 3

Raman laser and far infrared spectra of As₂S_x glasses with x ? 3 are given and discussed. The purpose of the work is to bring a vibrational spectroscopic contribution to the study of these glasses and to the hypothesis, still under discussion in the literature, that they might be constituted either by a homogeneous vitreous phase or by a mixture of As₂S₃ and As₄S₄.Our results confirm a phase separation, with formation of ß-As₄S₄, below a certain value of x, which depends not only on the preparation method of the samples but also on other factors such as melting time. Laser irradiation of ß-As₄S₄ modifies its Raman spectrum. Such a phenomenon is attributable to two principal factors, either a partial polymerization or formation of a species richer in arsenic. A structural and formation model of the As₂S_x glasses is given, starting from a more generalized structural model of vitreous As₂S₃ which is an accord with the vibrational results and those by the diffraction method in the literature.     

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.     

Preparation and properties of europium-doped phosphosilicate glasses obtained by the sol–gel method

In this work, we report the synthesis of europium-doped phosphosilicate glasses from tetraethylorthosilicate (TEOS), phenyltrietoxysilane (PTES) and ammonium phosphate (NH₄H₂PO₄) prepared by the sol–gel process. The matrix was synthesized by modified Stöber methodology. The alkoxide precursors PTES and TEOS were mixed with NH₄H₂PO₄, in the presence of europium III chloride, using ethanol as solvent in basic catalysis. These materials were studied by photoluminescence spectroscopy (PL), thermal analysis (TGA/DTA), transmission electron microscopy (TEM) and energy-dispersive spectroscopy (EDS). The results obtained for the materials show the formation of conchoidal-fractures, which are characteristics of glass materials. The thermal analysis showed the thermal stability of materials up to 300 °C. Eu III has been used as structural probe due to its photophysical properties. The PL spectra displays the lines characteristics of the Eu (III) ion ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3 and 4). Wide bands were observed, indicating non-homogeneous sites that are characteristic of amorphous systems.     

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.     

Hardness and refractive index of Ca–Si–O–N glasses

Vickers hardness and refractive index was determined for Ca–Si–O–N glasses with 14.6–58 e/o N and 19–42 e/o Ca. By applying slow cooling rates, transparent glasses were obtained for compositions near Ca_9.94Si₁₀O_17.73N_8.14, while the majority of the glasses were opaque due to small inclusions of elemental Si and/or Ca-silicide. Determined glass densities varied between 2.80 and 3.25 g/cm³. Hardness was found to vary from 7.3 to 10.1 GPa at a load of 500 g and, respectively increase and decrease linearly with N and Ca content. The refractive index was found to increase linearly with N content from 1.62 to 1.95 and showed no significant dependence on Ca content.     

Composition dependence of the glass transition temperatures of PdNiP and PtNiP glasses

Thermal properties of glassy PdNiP and PtNiP alloys have been measured as a function of the concentration of transition metals. The glass transiion temperature, T_g, of these alloys glasses exhibits a negative linear deviation with transition metal content - which is in contrast to the increasing T_g of binary glassy alloys with increasing metalloids.It is suggested that the suppression of the glass transition temperature of these glassy alloys may be attributed to the excess configurational entropy of disorder associated with a mixture of hard spheres differing in radius. In contrast, the increasing T_g of binary glassy alloys with the metalloid content may be associated with the short-range order resulting from strong interactions between metal and metalloid atoms.     

Effect of rare-earth elements on the plasma etching behavior of the RE–Si–Al–O glasses

The effect of rare-earth elements on the plasma etching behavior of oxide glasses were investigated to develop the window glass for a plasma processing chamber in the semiconductor industry. Aluminosilicate glasses with various rare-earth elements (Y, Gd and La) were prepared and their optical transmittance and plasma etching depth were evaluated. The plasma etching behavior of the glasses was estimated by X-ray photoelectron spectroscopy analysis at the fluorine plasma exposure surface of the glasses. The rare-earth element in the glass was highly related to various properties such as density, molar volume, mechanical properties and plasma etching depth. The cationic field strength of the rare-earth element more strongly affected the plasma etching depth of the glasses than the sublimation point of the fluorine compounds and this may be related to the plasma etching condition.     

Spectroscopic properties and ab initio calculations on the structure of erbium–zinc-borate glasses and glass ceramics

Glasses in the (Er₂O₃)_x·(B₂O₃)_(60 ? x)·(ZnO)₄₀ system (0 ≤ x ≤ 15 mol%) have been prepared by the melt quenching technique. X-ray diffraction, FTIR spectroscopy, UV-VIS spectroscopy and ab initio calculations studies have been employed to study the role of Er₂O₃ content on the structure of the investigated glass system.X-ray diffraction and infrared spectra of the glasses reveal that the B–O–B bonds may be broken with the creation of new non-bridging oxygen ions facilitating the formation of Er–O–B linkages. The excess of oxygen can be accommodated in the network by the conversion of sp² planar [BO₃] units to the more stable sp³ [BO₄] tetrahedral structural units. The linkages of the [BO₄] structural units can polymerize in [B₃O₉]^? 9 cyclic trimeric ions which will produce the ErBO₃ crystalline phase. An increase of the efficiency corresponding to the ⁴I_15/2 state to ⁴I_11/2 state (4f–4f) transitions of Er^+ 3 ions was observed for the erbium oxide richest glasses.Ab initio calculations on the structure of the matrix network show the thermodynamic instability of the [BO₄], [ZnO₄] and [Zn₄O] structural units. Formation of three-coordination oxygens was necessary to compensate shortage of oxygens from zinc ions.     

The effect of ionic and metallic silver on the crystalline phases developed in CaO–Al2O3–TiO2–P2O5 glasses

Development of crystallization in the CaO–Al₂O₃–TiO₂–P₂O₅ system glasses was investigated in the presence of ionic and metallic silver. Differential thermal analysis, X-ray diffractometry, ultra violet–visible spectrophotometry, atomic force microscopy and scanning electron microscopy were used to evaluate the resulted glasses and glass-ceramics. It was found that silver ions facilitated crystallization by decreasing the viscosity of the glasses. However, metallic silver, which was formed through heat treatment in hydrogen atmosphere, improved heterogeneous crystallization of the reduced glasses in the subsequent heat treatment. The preformed metallic silver led to effective crystallization of calcium titanium phosphate (CaTi₄(PO₄)₆), calcium metaphosphate (Ca(PO₃)₂) and calcium pyrophosphate (Ca₂P₂O₇) phases at significantly decreased temperatures. The two latter phases were partially dissolved out by leaching in acidic solution and left out a porous structure of calcium titanium phosphate glass-ceramic.     

Effects of Zn addition on the improvement of glass forming ability and plasticity of Mg–Cu–Tb bulk metallic glasses

The effects of Zn addition on the glass forming ability and mechanical properties of Mg₆₅Cu_25?xZn_xTb₁₀ (x = 0, 2.5, 5, and 7.5) have been investigated. We show that small amounts of Zn addition improve the glass forming ability, strength, and ductility of the Mg–Cu–Tb bulk metallic glass. For the best glass forming composition, amorphous rods of Mg₆₅Cu₂₀Zn₅Tb₁₀ with a diameter of at least 7 mm have been prepared by a conventional copper mold casting method. Additionally, this composition exhibits obvious yielding and plastic deformation upon quasi-static compressive loading. The fracture strength, total strain to failure, and the plastic strain of the Mg₆₅Cu₂₀Zn₅Tb₁₀ bulk metallic glass reaches 1025 MPa, 2.05% and 0.15%, respectively. This is significantly superior compared to that exhibited by the original Zn-free Mg–Cu–Tb amorphous alloy.     

Preparation and properties of chalcogenide glasses in the GeS2–Sb2S3–CdS system

In searching for new kind of photoelectric material, chalcogenide glasses in the GeS₂–Sb₂S₃–CdS system have been studied and their glass-forming region was determined. The system has a relatively large glass-forming region that is mainly situated along the GeS₂–Sb₂S₃ binary side. Thermal, optical and mechanical properties of the glasses were reported and the effects of compositional change on their properties are discussed. These novel chalcogenide glasses have relatively high glass transition temperatures (T_g ranges from 566 to 583 K), good thermal stabilities (the maximum of deference between the onset crystallization temperature, T_c, and T_g is 105 K), broad transmission region (0.57–12 μm) and large densities (d ranges from 2.99 to 3.34 g cm^?3). These glasses would be expected to be used in the field of rare earth doped fiber amplifiers and nonlinear optical devices.     

On the origin of the high Kerr coefficient measured in thallium–zinc–tellurite glasses

Measurements of Kerr electrooptical sensitivity of several zinc–thallium–tellurite glasses are presented, and composition dependence of Kerr sensitivity is compared with the dependence of the second harmonic generation efficiency collected for optically poled TeO₂–TlO_0.5–ZnO glasses. These data being analyzed jointly with Raman measurements data allowed us to conclude that the high electrooptical Kerr coefficient and nonlinearity of Tl₂O–ZnO–TeO₂ glasses, and their sharp increase with augmenting concentration of thallium oxide TlO_0.5 above 15% should be attributed to the presence of Tl⁺ cations having very high non-linear polarizability most likely related to their electronic lone pairs.     

Electrical and dielectric properties of MnF2–ZnF2–NaPO3 glasses

Direct electrical conductivity and dependencies of complex electrical modulus vs. temperature and frequency have been measured on glasses from the MnF₂–ZnF₂–NaPO₃ system. These glasses are sensitive to atmospheric humidity and as a consequence, the electrical conductivity increases up to temperature of 50 °C. A hydrated layer is created by the effect of water and leads to the significant increase of the electrical conductivity in the case of 0MnF₂–20ZnF₂–80NaPO₃ glass. This behavior is governed by Arrhenius relation where the values of activation energy are increasing and values of the electrical conductivity are decreasing with the amount of MnF₂. Dielectric measurements show that a heterogeneous phase is formed in the bulk of glasses. This may be seen when plotting complex electrical modulus in the complex plane. The records made by the light microscope confirmed the occurrence of the other phase in the bulk of glasses.