EPR and optical studies on binary mixed alkali-alkaline earth oxide borate glasses doped with Cu<Superscript>2+</Superscript> ions

Mixed alkali alkaline earth oxide borate glasses of the composition (25 – x)Li₂O–xK₂O–12.5BaO–12.5MgO–49B₂O₃–1CuO (x = 0, 5, 10, 15 and 20 mol %) were prepared by the melt quenching technique. The X-ray diffractograms of all the glass samples were recorded at room temperature. Peak free X-ray spectra revealed the amorphous nature of all the prepared glasses. Modulated differential scanning calorimetry (MDSC) was used to determine the glass-transition temperature (T _g ). The probable mixed alkali effect was investigated using experimental techniques like density, molar volume, MDSC, electron paramagnetic resonance (EPR), and optical absorption studies. From the EPR spectra the spin-Hamiltonian parameters were evaluated. The spin-Hamiltonian parameter values indicated that the ground state of \(C{u^{2 + }}is{\kern 1pt} {d_{{x^2} - {y^2}}}\) orbital (²B_1g) and the site symmetry around Cu² is tetragonally distorted octahedral. The variation of g _|| and A _|| as a function of Li₂O content was found to be nonlinear. A broad optical absorption band was observed in all the glasses containing Cu² ions corresponding to ²B_1g → ²B_2g transition. From the optical absorption studies the values of the optical band gap (E _opt) for indirect, direct transitions and Urbarch energy (ΔE) have been evaluated. By co-relating the EPR and optical absorption data, bonding parameters α², β² and β ₁ ² were evaluated.     

Effect of Li<Subscript>2</Subscript>O on the Refractive Index and Optical Band Gap of Cadmium Phosphate Glasses

A series of lithium cadmium phosphate glasses having composition (mol %) xLi₂O-(50 ? x)CdO-50P₂O₅ were prepared in a platinum crucible by the melt quenching technique. The quantity x varies in the range 0–40. The mass density and refractive index of these glasses were found in the ranges 3.95–2.89 g/cm₃ and 1.55–1.40, respectively. The optical absorbance studies were also carried out on these glasses to measure their energy gaps. The absorption spectra of these glasses were recorded in the UV-visible range. No sharp edges were found in the optical spectra, which verifies the amorphous nature of these glasses. The optical band gap energies for these glasses were found to be in the range 2.58–3.5 eV. It was observed that the density, the refractive index, and the optical band gap energy decrease with increasing amount of lithium oxide. The band tailing, worked out from the Urbach plots, shows an increase with increasing Li₂O content and lies in the range 0.47–0.78 eV. The absorption coefficient is observed to show an exponential dependence on the photon energy.     

Parameters of luminescence and the local structure of Eu<Superscript>3+</Superscript> centers in fluorogermanate glasses

The influence of the chemical nature of the local environment of Eu³⁺ ions on the parameters of luminescence of these centers in glasses of the (BaGeO₃)_{1 ? x ? y} (Al₂O₃) _x (0.45CaF₂ · 0.55MgF₂) _y (x = 0.25, y = 0; x = 0.17, y = 0.17; x = 0.15, y = 0.22; x = 0.07, y = 37.00; x = 0, y = 0.45) system is investigated. The oxidation state of europium atoms and the degree of homogeneity of their local environment in the glasses are determined using ¹⁵¹Eu Mössbauer spectroscopy.     

Observation of Meyer-Neldel relation for non-isothermal crystallization in Se<Subscript>70</Subscript>Te<Subscript>30</Subscript> and Se<Subscript>70</Subscript>Te<Subscript>28</Subscript>M<Subscript>2</Subscript> (M = Ag,Sb, Zn) glasses

In the present paper, we report the applicability of Meyer-Neldel rule for pre-exponential factor of non-isothermal crystallization in Se₇₀Te₃₀ and Se₇₀Te₂₈M₂ (M = Ag, Sb, Zn) glasses using DSC technique. We have observed strong correlation between pre-exponential factor K ₀ and activation energy of non-isothermal crystallization E _c for the present glasses.     

Effects of co-ion initial concentration ratio on removal of Pb<Superscript>2+</Superscript> from aqueous solution by modified sugarcane bagasse

A modified sugarcane bagasse (SCB) fixed bed column was used to remove Pb²⁺ from aqueous solution. To determine the optimal condition for Pb²⁺ separation, Ca²⁺ was chosen as the model interfering ion, and effects of Ca²⁺ and Pb²⁺ initial concentration ratio (C ₀ ^Ca : C ₀ ^Pb ) on the adsorption of Pb²⁺ were investigated. Results showed that adsorption amount ratio of Ca²⁺ and Pb²⁺ (q _e ^Ca : q _e ^Pb ) had a good linear relationship with C ₀ ^Ca : C ₀ ^Pb . Mass ratio of Pb²⁺ absorbed on the modified SCB was higher than 95% at C ₀ ^Ca : C ₀ ^Pb <1.95, illustrating that Pb²⁺ could be selectively removed from aqueous solution. To verify that, simulated waste water containing co-ions of K⁺, Na⁺, Cd²⁺ and Ca²⁺ was treated, and results showed that the equilibrium amount of Pb²⁺, K⁺, Na⁺, Cd²⁺ and Ca²⁺ adsorbed was 134.14, 0.083, 0.058, 1.28, and 1.28mg g^?1, respectively, demonstrating that the modified SCB could be used to remove Pb²⁺ from aqueous solution in the investigated range.     

SHS-produced Co<Superscript>2+</Superscript>Ti<Superscript>4+</Superscript>-doped barium and strontium hexaferrites: Static and dynamic magnetic properties

Static and dynamic magnetic properties of SHS-produced BaFe_12–2x (Co _х Ti _х )O₁₉ (х = 1.0, 1.1, 1.2) and SrFe_12–2y (Co _y Ti _y )O₁₉ (0 ≤ y ≤ 1.0) hexaferrites were characterized by magnetization and FMR measurements. Dynamic properties of SrFe_12–2y (Co _y Ti _y )O₁₉ hexaferrites were rationalized in terms of not only magnetic anisotropy but also the anisotropy of magnetomechanical ratio. SHS-produced ferrites can be recommended for designing radar-absorbent coatings and other SHF devices operating in the range 20–50 GHz.     

X-ray Fluorescence of Eu<Superscript>3+</Superscript> Ions in Glassy and Polycrystalline Lithium Tetraborate

The X-ray-luminescence spectra of glassy and polycrystalline lithium tetraborate Li₂B4O₇ activated by europium oxide Eu₂O₃ are studied in the spectral range of 200 to 800 nm. The luminescence observed in the wavelength region of 570 to 720 nm is caused by intraconfiguration f–f electron transitions between the levels of the first excited multiplet ⁵D and the main multiplet ⁷F of the Eu³⁺ ion.     

Optical Investigation of Sm<Superscript>3+</Superscript> Doped in Phosphate Glass

Samarium doped zinc-magnesium-phosphate glasses having composition (60 – x)P₂O₅–10MgO–30ZnO–xSm₂O₃ where x = 0.1, 0.3, 0.6, 1.0 mol % were prepared by melt quenching technique. Archimedes method was used to measure their densitieswhich are lying in the range 2.65–2.91 g/cm³. On the basis of the increasing trend in the density while increasing the content of Sm₂O₃ it can be concluded that the bridging oxygen is converted to non-bridging oxygen The UV-Vis absorption spectroscopy was carried on in the wavelength range 310–900 nm where the absorption spectra consist of six absorption peaks corresponding to the transitions from the ground state ⁶H_5/2 to various excited energy levels. The optical band gaps are calculated to be 3.93–4.41 eV, 3.31–3.73 eV and 0.27–0.29 eV for direct band gap, indirect band gap and Urbach energy, respectively. The physical parameters like oxygen packing density, refractive index, molar refractivity, metallization, and electronic polarizability are also studied. The Differential Scanning Calorimetry (DSC) technique is used to evaluate the thermal stability.     

Cluster Self-Organization of Intermetallic Systems: Two-Layer Quasi-Spherical Nanocluster Precursors K69 and K26 in the Crystal Structure of Li<Subscript>26</Subscript>Na<Subscript>58</Subscript>Ba<Subscript>38</Subscript> (<Emphasis Type="Italic">cF</Emphasis>488)

The geometric and topological analysis of the crystal structure of intermetallic Li₂₆Na₅₈Ba₃₈ (cF488, a = 27.335 Å, V = 20 424 ų, F-43m) is carried out using computer methods (ToposPro software package). The analysis method is based on determining the chemical composition and structure of an intermetallic cluster precursor and constructing a basic 3D network of the structure in the form of a graph whose nodes correspond to the position of their centers of gravity. Using the method of the complete decomposition of the 3D factor graph of the crystal structure into cluster substructures, we find two types of framework-forming nanoclusters, namely, K69 of the 1@16@52 composition and K26 of the 0@4@22 composition with point symmetry g =–43m. The symmetric and topological code of self-assembly of 3D structures from nanocluster precursors is reconstructed in the following form: primary chain → microlayer → microframework. Clusters Ba5, Na₆(Na₄), and Na₂В are determined as spacers occupying voids in the 3D framework of nanoclusters K69 and K26.     

Synthesis of Titanates with a Ramsdellite-Type Tunnel Structure Crystallizing in the Li<Subscript>2</Subscript>O-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> System in Different Gaseous Media

The ramsdellite-type phases crystallizing in the Li₂O-Fe₂O₃-TiO₂ system in the course of synthesis in gaseous media at different oxygen partial pressures are studied. Solid solutions based on the ramsdellite structure with the composition Li₂Ti_3?xFe _x O_{7 ? δ} (0 ≤ x ≤ 0.7) are prepared in an oxidizing medium (P_O2 = 1 atm) for the first time. Analysis of the results obtained by electron paramagnetic resonance and Mossbauer spectroscopy revealed that, in these solid solutions, all iron ions are in the oxidation state Fe⁺³.     

Gamma and neutron shielding characterizations of the Ag2O–V2O5–MoO3–TeO2 quaternary tellurite glass system with the Geant4 simulation toolkit and Phy-X software

Gamma and neutron shielding potential of the newly developed xAg₂O-(35-x)[0.5V₂O₅-0.5MoO₃]-65TeO₂ (x = 0, 5, 10, 15, 20 and 25 mol%) quaternary tellurite glass system were investigated computationally by means of Geant4 Monte Carlo simulations and Phy-X software. Gamma ray shielding capabilities were studied via the mass attenuation coefficient (μ_m), transmission fractions (T), effective atomic number (Z_eff), half value layer (HVL) and mean free path (MFP) parameters and for the photon energies of 0.284, 0.356, 0.511, 0.662, 1.173 and 1.330 MeV. Fast neutron removal cross-section (∑_R) parameter of the glasses was calculated to assess the neutron shielding capabilities. The results of this study revealed that tellurite glass containing 25% moles of Ag₂O has highest μ_m and Z_eff and lowest T, HVL and MFP values due to the high atomic number of Ag. In this study it was also seen that the ∑_R of the investigated glass system increases with the increase of Ag₂O fraction and ∑_R values of the studied glasses are higher than barite added concrete and close to the ∑_R of the PbO added borate glasses.     

Thermal expansion and phase transitions in K<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Rb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>BSi<Subscript>2</Subscript>O<Subscript>6</Subscript> leucite borosilicate solid solutions

Continuous solid solutions and the reversible phase transition from the I-43d cubic phase to the Ia-3d cubic phase are revealed in the borosilicate series K_{1 ? x} Rb _x BSi₂O₆. Samples in the KBSi₂O₆-RbBSi₂O₆ system are prepared by solid-phase synthesis and crystallization of glasses and investigated using the annealing and quenching technique, high-temperature X-ray diffraction, and dilatometry. The above polymorphic phase transition is observed in all solid solutions at temperatures in the range from 330 to 430°C depending on the composition: an increase in the rubidium content in the solid solution leads to a gradual decrease in the phase transition temperature. The linear thermal expansion coefficients α are determined for solid solutions of different crystalline modifications and glasses. The linear thermal expansion coefficients α for the I-43d low-temperature phase are equal to (20–23) × 10^?6 K^?1 according to the X-ray diffraction data and (21–24) × 10^?6 K^?1 according to the dilatometric data. The values of α for the Ia-3d high-temperature phase lie in the range (4–9) × 10^?6 K^?1 according to the X-ray diffraction data and in the range (6–9) × 10^?6 K^?1 according to the dilatometric data. The linear thermal expansion coefficients for both modifications decrease with an increase in the rubidium content in the solid solutions. The linear thermal expansion coefficients for glasses α = (10–11) × 10^?6 K^?1 are close to those for the high-temperature modification and virtually independent of the sample composition. The I-43d (cubic) ai I4₁/a (tetragonal) o Ia-3d (cubic) polymorphic phase transitions in the KBSi₂O₆ compound are revealed by differential scanning calorimetry (DSC) and dilatometry. Their reversibility is confirmed by the DSC data.     

Crystal structure of Pb<Subscript>6</Subscript>O[(Si<Subscript>6</Subscript>Al<Subscript>2</Subscript>)O<Subscript>20</Subscript>]

The crystal structure of Pb₆O[(Si₆Al₂)O₂₀)] is investigated using X-ray diffraction. The compound has tetragonal symmetry, space group I4/mmm, a = 11.7162(10) Å, c = 8.0435(12) Å, and V = 1104.13(2) ų. The structure is refined to R ₁ = 0.036 for 562 unique reflections with [F ₀] ≥ 4σF. The structure contains two symmetrically independent positions of the Pb²⁺ cations coordinated by five O atoms (Pb²⁺-O^2? = 2.34–2.68 Å). The TO₄ tetrahedra (T = Si, Al) form tubular [(Si₆Al₂)O₂₀] chains extended along the c axis. The O₄ oxygen atom is not bonded to the Si and Al atoms and is octahedrally coordinated by six Pb atoms with the formation of an oxo-centered OPb₆ octahedron. The assumption is made that, in some of lead silicate and aluminosilicate glasses, a number of oxygen atoms are located outside the tetrahedral structure and represent segregation centers of the Pb²⁺ cations due to the formation of oxo-centered complexes.     

Synthesis and investigation of Ag-Cs-<Emphasis Type="Italic">X</Emphasis> (<Emphasis Type="Italic">X</Emphasis> = I,Br, Cl) glasses doped with Er<Superscript>3+</Superscript>

The glass formation and crystallization of ErI₃-doped melts in the Ag-Cs-Pb-X (X = I, Br, Cl) are investigated in the section corresponding to the cation ratio Ag: Cs: Pb = 59: 39: 2 with ErI₃ contents of 0.2–7.5 mol %. The glass transition, crystallization, and melting temperatures are determined for a number of compositions. The primary crystalline phases that precipitate from melts upon crystallization are identified. It is demonstrated that the iodide, bromide, and chloride glasses containing up to 0.5 mol % ErI₃ have the lowest crystallization ability. An increase in the ErI₃ content leads to the precipitation of unidentified erbium-containing phases from melts upon cooling and to an increase in the crystallization ability of glasses. The spectral and luminescence properties of the glass of the composition 52Ag · 17AgCl · 39CsBr · 2PbCl₂ + 0.5 mol % ErI₃ are studied in the range of the ⁴ I _13/2 → ⁴ I _15/2 transition of the Er³⁺ ion. It is found that the lifetime of the ⁴ I _13/2 → ⁴ I _15/2 level of the Er³⁺ ion is equal to 10 ms.     

AC Conductivity and Dielectric Behavior of Silicophosphate Glass Doped by Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>

Silicophosphate glasses of nominal composition (P₂ O ₅ 50%-SiO₂ 30%-Na₂O 20%) and Nd₂ O ₃ additive (0.5 and 2 wt%) were prepared and dielectric behavior has been studied over a temperature range (302–483 K) in the frequency range (0.5 - 3243 kHz). Frequency dependence of AC conductivity (σ _ac), has been explored using the universal power law. Disparity of the frequency exponent (s) with temperature was examined in terms of diverse conduction mechanisms. The principal conduction mechanisms were found correlated to both barrier hopping (CBH) and quantum mechanical tunneling (QMT) models. Temperature dependence of σ _ac (ω) showed a linear increase with different frequencies. In addition, the capacitance, loss tangent, dielectric loss and dielectric constant were calculated over variable temperature ranges and frequencies.     

Density and microhardness of glasses in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The density d at a temperature of 25°C is measured by the hydrostatic weighing method, the Vickers microhardness H _V is determined, and the fluctuation free volume fraction f _g is calculated for glasses in the SrO-B₂O₃-SiO₂ system with a constant strontium oxide content in the range from 35 to 45 mol %. It is demonstrated that the quantities H _V and f _g decrease and the density d increases with an increase in the SrO content.     

Optical Properties of Silver Halide Photochromic Glasses Doped with Cobalt Oxide

Photochromic glasses having composition (SiO₂)₄₅(B₂ O ₃)₃₅(Al₂O₃)_7.5(Na₂O)_12.5(AgBr), (Cu₂O) doped with (CoO) _x , in which, x = 0, 0.006, 0.02 and 0.07 g were prepared using the conventional melt technique. The amorphous nature of these glass samples was confirmed using X-ray diffraction analysis at room temperature. The absorption measurements in the infrared region of the spectrum were recorded in the wave number range (4000–400) cm^?1. Spectral reflectance and transmittance at normal incidence of the prepared glass samples were recorded with a spectrophotometer in the spectral range 200–2500 nm. Experimental and theoretical densities of the prepared glass samples were measured, calculated and compared. Analytical expressions were used to calculate the real and imaginary parts of the refractive indices. Dispersion parameters such as: single oscillator energy, dispersion energy, average oscillator wavelength, and Abbe’s number were deduced and compared. Absorption dispersion parameters such as: optical energy gap for direct and indirect transitions, Urbach energy and steepness parameter were calculated. Effects of doping with cobalt oxide CoO as a transition metal on linear and predicted nonlinear optical parameters were investigated and interpreted. Experimental results indicate that there is an optimum concentration of cobalt doping around 0.006 g. The optical band gap decreases with increasing doping and causes an increase in nonlinear optical parameters. Doping with cobalt oxide improves the linear and nonlinear optical properties of the prepared glasses.     

Glass formation in the ZrF<Subscript>4</Subscript>-BiF<Subscript>3</Subscript>-<Emphasis Type="Italic">Me</Emphasis>F (<Emphasis Type="Italic">Me</Emphasis> = Li,Na, K) fluoride systems

The glass formation in the ZrF₄-BiF₃-MeF (Me = Li, Na, K) systems is investigated. Bismuth fluorozirconate glasses are synthesized in this system, and their thermal and optical properties are described.     

Synthesis and crystal structure of the low-temperature modification of Li<Subscript>12</Subscript>Zn<Subscript>4</Subscript>(P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>5</Subscript>

The crystal structure of a low-temperature modification of the Li₁₂Zn₄(P₂O₇)₅ compound has been determined by full-profile analysis from the X-ray powder diffraction data. The compound crystallizes in the monoclinic crystal system (a = 5.130(1) Å, b = 13.454(1) Å, c = 8.205(1) Å, β = 90.36(1)°, space group P2₁/n, Z = 4) and has a framework structure in which the zinc and lithium atoms statistically occupy equivalent positions.     

Optical,Spectral, and Radiation-Shielding Properties of High-Lead Phosphate Glasses

The spectral, optical, physicochemical, radiative, and radiation-shielding properties of glasses in the PbO-P₂O₅-R _m O _n system (where R _m O _n stands for Group I–V element oxides) are investigated as a function of their composition. The composition of a colorless radiation-resistant high-lead glass suitable for production on a semicommercial scale is determined. The properties and optical quality parameters of the glass are studied. The new phosphate glass is a lead metaphosphate containing aluminum, alkali, and alkaline-earth oxides. This glass is resistant to radiation at doses up to 10⁷ R and has an optical transmission edge at 360 nm. The coefficient of absorption of gamma radiation for the new glass is larger than those of dense silicate flints. According to the optical parameters, the new glass lies between dense flints and dense barium flints in the Abbe diagram and compensates for the absence of the latter flints in catalogues of radiation-resistant glasses.