Physical Properties,Optical band gaps and Radiation Shielding Parameters Exploration for Dy<Superscript>3+</Superscript>-doped Alkali/Mixed Alkali Multicomponent Borate Glasses

Six compositions of 1 mol % Dy³⁺-doped multicomponent borate glasses containing single Li₂O, Na₂O, K₂O and mixed Li₂O–Na₂O, Li₂O–K₂O, and Na₂O–K₂O oxides have been synthesized by well-known melt-quenching technique. Following the measured density and refractive index values, various physical parameters were estimated for all the glass samples and differences in them are correlated with structural changes. To explore optical properties like absorption edge (λ_cut-off), optical band gap energy (E_opt), and Urbach energy (ΔE), optical absorption spectra were recorded for all the glasses. The E_g has been calculated using Davis and Mott theory for direct allowed, and indirect allowed transitions and the results were reported. The E_g values are also estimated using absorption spectrum fitting (ASF) method. The optical parameters variations have also been associated with the structural changes occurring in the glasses with different alkali/mixed alkali oxides content presence. The shielding properties of the prepared glasses were studied in terms of effective atomic numbers (Z_eff), mean free path (MFP), half value layer (HVL) and macroscopic effective removal cross-section (Σ_R). From these results, it was found that Potassium (K) glass shows superior gamma ray shielding properties due to a higher value of Z_eff and lower values of both MFP and HVL. These results indicate that the prepared glasses might be utilized in place of some common shielding materials to shield γ-rays and neutrons.     

On the critical displacement of excited kinetic units in liquids and glasses

The critical displacement of an atom (a group of atoms) in inorganic glasses Δr _m, which corresponds to the maximum of the interatomic attractive force, is calculated using available data on the surface tension and elastic constants. It is found that the critical atomic displacement Δr _m is close in order of magnitude to the linear dimension of the activation volume of atomic excitation v _h ^1/3 for glasses in the As-S and Ge-As-S systems with a chain structure and is considerably less than the value of v _h ^1/3 for alkali silicate glasses and glasses in the Cd-As system with a structure involving ionic sublattices. A relationship for calculating the activation volume of the atomic excitation from data on the glass transition temperature and elastic constants is derived within the model of an excited state.     

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.     

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.     

Change of the thermal behavior of 55Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 45B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass at annealing close to the vitrification temperature

The characteristic properties of relaxation processes for 55Bi₂O₃ ? 45B₂O₃ glass were described. The pattern of changes of the vitrification temperature (T _g ) is found to be quasi-periodic; the value of the endothermic effect near T _g (ΔC’ _p ) and the difference between the softening point and the vitrification temperature (T _m –T _g ) were determined. The temperature-time parameters of the transition from quasi-periodic to the continuous change of the properties were determined and an explanation of such behavior of the system was offered.     

Problems of compatibility of the values of glass transition temperatures published in the world literature

The influence of different factors (primarily, the temperature-time conditions for preparation and measurement of samples) on the glass transition temperatures determined from the temperature dependences of properties is analyzed using the calculations performed in terms of the relaxation theory of glass transition. The most optimum conditions for measurement of the glass transition temperatures T _g that ensure the compatibility of the values of T _g obtained by different researchers are recommended. The validity of the assertion that the glass transition temperature T _g is a temperature at which the viscosity of glasses is equal to 10¹³ P is considered.     

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.     

Crystal structure and thermal expansion of ammonium pentaborate NH<Subscript>4</Subscript>B<Subscript>5</Subscript>O<Subscript>8</Subscript>

Anhydrous ammonium pentaborate NH₄B₅O₈ has been synthesized by thermal dehydration of larderellite NH₄[B₅O₇(OH)₂] · H₂O at a temperature of 290°C for 7 h. The crystal structure has been determined from the X-ray powder diffraction data: a = 7.58667(5) Å, b = 12.00354(8) Å, c = 14.71199(8) Å, R _p = 6.23, R _wp = 7.98, R _B = 12.7, R _F = 8.95, and β-KB₅O₈ structure type. The double interpenetrating framework is formed by pentaborate groups, each consisting of a boron-oxygen tetrahedron and four triangles, in which all oxygen atoms are bridging. The thermal behavior of the NH₄B₅O₈ compound has been investigated using thermal X-ray diffraction. As for other pentaborates of this type, the thermal expansion of the NH₄B₅O₈ compound is anisotropic and reaches a maximum along the a axis. The thermal expansion coefficients are as follows: α _a = 39 × 10^?6, α _b = 6 × 10^?6, α _c = 20 × 10^?6, and α _V = 65 × 10^?6 °C^?1.     

Effect of iron oxide (Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>) on the structural,optical, electrical,and dielectric properties of SrO–V<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

The oxide glass system of the composition (10 – x)SrO–xFe₂O₃–90V₂O₅, (x = 0, 2, 4, 6 and 8 mol %) were prepared by a standard melt quenching technique. The amorphous nature of the prepared glass was confirmed using X-ray diffraction technique. The infrared spectra of these glasses were recorded over a continuous spectral range (850–1500 cm^–1). The density of prepared sample was obtained by the Archimedes principle. The physical parameters of the glasses were also determined with respect to the composition. Density increases from 3.10 to 3.20 g/cm³, whereas the molar volume decreases with the increase in Fe₂O₃ concentration. In order to study optical properties, absorption spectra were measured at room temperature. Indirect optical energy band gap, optical dielectric constant, refractive index were calculated from optical energy band gap. The refractive index decreases gradually with the increase in Fe₂O₃ content due to increase of bridging oxygen’s. For temperatures from 300 to 500 K, the dc conductivity increased with the increasing Fe₂O₃ content. The dielectric properties like dielectric constant, dielectric loss factor and dielectric loss tangent investigated at the room temperature in the frequency range of 10 kHz to 1 MHz decreases with frequency. The dielectric behavior shows strong frequency as well as composition dependence.     

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.     

Structure-Property Relations in Barium Borate Glasses from Raman Scattering Data

Glasses in the xBaO-(100 ? x)B₂O₃ system (x = 16–50 mol %) are investigated by Raman spectroscopy. The spectral forms of stoichiometric groupings are separated from the experimental Raman spectra. The diagram of the content of these groupings in glasses is constructed. The diagram obtained makes it possible to calculate the densities, refractive indices, temperature coefficients of linear expansion, and fractions of four-fold-coordinated boron atoms with the use of the experimentally determined partial properties of the groupings. It is revealed that the dependences of the boson peak intensity, the boson peak frequency, and the glass transition temperature on the composition of glasses in the barium borate system correlate with each other.     

Raman spectra and surface structure of CaO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass leached in potassium hydroxide solutions

It is difficult to research on the surface structure of amorphous phase in fly ash during leaching reaction due to crystalline phase and complex structure. In the present work, in order to reveal the effects of leaching reaction on the surface structure of amorphous phase in fly ash, the modelling CaO-Fe₂O₃-Al₂O₃-SiO₂ glass was prepared by the traditional melting methods. The leaching reaction of CaO-Fe₂O₃-Al₂O₃-SiO₂ glass with 7.5 M KOH was investigated by spectroscopy, spectrophotometer and wet chemical method. The results show that the content of Q ¹, Q ², Q ³ and Q ⁴ of glass without corrosion was 4.21, 9.51, 23.03 and 52.55%, respectively, which shows that the network polymerization of glass is compact. The leaching reaction of glass can be described by the following equation: dS/dt = k/(r + S ₀). Leaching in KOH for various times induces the content of Q ⁴ and Q ¹ to be decreased, and Q ² and Q ³ increased, resulted in the depolymerization of network and the surface glass dissolved in alkaline solution to form a gel phase. In stage one of leaching reaction, the rate of iron ion leached from glass surface was slow, which resulted in the small slope of straight-line relationship of leaching curve. In the following stage, the leaching rate of iron ion increased with the prolongation of time.     

Optical glass-ceramics based on fluorine-containing silicate glasses doped with rare-earth ions

Oxyfluoride silicate glasses in the SiO₂-Al₂O₃(AlF₃)-CdF₂-PbF₂-ZnF₂-Eu₂O₃ system are studied. Glass-ceramic materials with special properties promising for use of these glass-ceramics as active optical media are synthesized from the oxyfluoride glasses under investigation. The physicochemical and spectral-luminescence properties of the glass-ceramic materials synthesized are investigated. It is shown that the composition of glasses and, consequently, their thermal and physical properties depend on the synthesis conditions. Heat treatment of glasses doped with Eu³⁺ ions at temperatures somewhat higher than the glass transition point T _g leads to the formation of β-PbF₂ nanocrystals such that the major part of the dopant enters into the nanocrystal composition.     

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,Characterization and <Emphasis Type="Italic">In Vitro</Emphasis> Biological Evaluation of Sol-gel Derived Sr-containing Nano Bioactive Glass

In this study, bioactive glass of the type SiO₂–CaO–SrO–P₂O₅ was obtained by the sol-gel processing method and the effects of SrO/CaO substitution on the in vitro biological properties of the synthesized glasses were evaluated. The obtained bioactive glasses were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), differentioal scanning caloremetry (DSC) and Brunauer, Emmett and Teller (BET) analyses. The effects of various glass compositions on proliferation and differentiation of osteoblastic cells were also evaluated. The results showed that incorporation of Sr in the obtained glass network did not result in any structural alteration due to the similar role of SrO compared with that of CaO. In vitro experiments with human osteosarcoma cell lines (MG-63) indicated that bioactive glass incorporating 5 mol % in the composition revealed optimal cell proliferation and alkaline phosphatase (ALP) activity. Our results ascertained this material to be non-toxic and compatible for the proposed work in segmental defects in the rabbit model in vivo.     

Photon interaction parameters for some ZnO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Some photon interaction parameters such as mass attenuation coefficient, effective atomic number, half value layer, mean free path and electron density for 15ZnO–(17.5–x)Al₂O₃–xFe₂O₃–67.5P₂O₅ glass system (x = 0, 7.5, 12.5, 17.5) and 15ZnO–(25–x)Al₂O₃–xFe₂O₃–60P₂O₅ glass system (x = 0, 25) have been investigated in the photon energy range of 1 keV to 100 GeV. It has been observed that all the photon interaction parameters for the selected glass systems vary with the photon energy. Among the selected glass systems, the sample 15ZnO–25Fe₂O₃–60P₂O₅ glass system shows maximum values for mass attenuation coefficients, effective atomic numbers, electron densities and minimum values for mean free path and half value layer in the entire energy grid.     

Thermal behavior of layered perovskite-like compounds in the Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>-BiFeO<Subscript>3</Subscript> system

The thermal properties of compounds of the general formula Bi _{m + 1} Fe _{m ? 3} Ti₃O_{3m + 3}, which are layered perovskite-like phases of the Aurivillius type, are investigated as a function of their composition. It is demonstrated that the temperature of decomposition of the Bi _{m + 1} Fe _{m ? 3} Ti₃O_{3m + 3} compounds decreases with an increase in the thickness of perovskite-like layers alternating in the structure and that the composition dependence of the temperature of the structural transition observed in these compounds exhibits a more complex behavior. The linear thermal expansion coefficients of all the compounds under investigation are found to be virtually independent of the composition.     

Stability of polymer structures based on fullerene C<Subscript>60</Subscript> under their oxidation with oxygen

A comparative study of the oxidative destruction of the monomer face-centered cubic (FCC) lattice and various polymer [dimeric (D), orthorhombic (O), tetragonal (T), and rhombohedral (R)] phases of C₆₀ in an atmosphere of oxygen has been performed in the temperature range of 100–500°C with the use of a flow microunit connected to a gas chromatograph. From direct measurements of the content of CO₂ in the gaseous products of destruction, the temperature dependences of oxidation rates are measured for the materials under study. It has been established that, with respect to stability against oxidative destruction, different forms of C₆₀ may be arranged as follows: the monomer FCC phase of C₆₀ > D > O > T > R. The reasons behind this tendency are discussed.     

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.     

Ultrasonic velocity measurements in isobutyric acid - water binary mixtures over the temperature range from 300.15 to 313.15 K

We measured the ultrasonic velocity, U, density, ρ, and viscosity, η in Isobutyric acid - water binary liquid mixtures over the entire composition range at temperatures ranging from 300.15 to 313.15 K under atmospheric pressure. The experimental data values were analyzed to determine, various acoustical parameters: adiabatic compressibility, β, acoustic impedance, Z, free length, L_f, free volume, V_f, molar volume, V_m, relaxation time, τ, absorption coefficient, α/f², internal pressure, π_i, Gibb’s free energy, ΔG, cohesive energy, CE, Wada’s constant, W, Rao’s constant, R_m and relative association, R_A. The variation of these parameters versus the mixture composition was explained on the basis of the intermolecular interactions between the components of the mixture.