Compositional dependence of in-vitro bioactivity in sodium calcium borate glasses

Borate glasses with composition xCaO (100−x) B₂O₃ (20≤x≤50), where x is in mole percent) and 50CaO·45B₂O₃·5Na₂O have been prepared using conventional melt quench technique. Samples were submerged in simulating body fluid solution (SBF) at 37 °C for various periods of time. After storage the samples were analyzed in order to investigate if a surface layer of hydroxyl carbonate apatite layer (HCA layer/Ca-P layer) had formed. The analysis technique used included Fourier-Transform Infrared Spectroscopy (FTIR). The rate of HCA layer formation on the surface of exposed glass samples is determined by FTIR, percentage weight loss measurements of glass samples in SBF and variation of pH of SBF as a function of time. Increase in calcium content in the glass matrix has shown to decrease the rate of HCA formation on glass surfaces. The borate glass with x=20 has shown HCA layer formation on glass surface within two days of dipping. The bone like apatite formation of glass surface demonstrates the potential of glass for integration with bone.     

Compositional-dependent lead borate based glasses doped with Eu ions: Synthesis and spectroscopic properties

New multicomponent lead borate based glasses with various PbO/B₂O₃ weight ratio were prepared. The glass samples were analyzed in detail by using Raman and IR absorption spectroscopy. Optical properties of Eu³⁺ ions have been investigated in lead borate based systems, in which PbO/B₂O₃ weight ratios were changed from 1:2 to 8:1 in glass composition. The values of the phonon energy of the host and ⁵D₀ lifetime of Eu³⁺ decrease, whereas absorption and emission intensities, as well as bonding parameter increase with increasing PbO concentration. Additionally, spectral lines are shifted in direction to the lower frequency region. Non-monotonic dependence of the fluorescence intensity ratio R (⁵D₀-⁷F₂/⁵D₀-⁷F₁) upon PbO/B₂O₃ content has been observed in contrast to bonding parameter that is also non-linear but monotonic. Some structural and spectroscopic aspects for Eu-doped lead borate based glasses are presented.     

Spectroscopic and photoluminescence characteristics of Dy ions in lead containing sodium fluoroborate glasses for laser materials

Lead containing calcium zinc sodium fluoroborate (LCZSFB) glasses doped with different concentrations of trivalent dysprosium ions were prepared and investigated by the XRD, FTIR, optical absorption, photoluminescence and decay curve analysis. The experimentally determined oscillator strengths have been determined by measuring the areas under the absorption peaks and the Judd–Ofelt (J–O) intensity parameters were calculated using the least squares fit method. From the evaluated J–O parameters the radiative transition probability rates, radiative lifetimes and branching ratios were calculated for ⁴F_9/2 excited level. Room temperature photoluminescence spectra for different concentrations of Dy³⁺-doped LCZSFB glasses were obtained by exciting the glass samples at 386 nm. The intensity of Dy³⁺ emission spectra increases with increasing concentration of 0.1, 0.25, 0.5 and 1.0 mol% and beyond 1.0 mol% the concentration quenching is observed. The measuring branching ratios are reasonably high for transitions ⁴F_9/2→⁶H_15/2 and ⁶H_13/2, suggesting that the emission at 484 and 576 nm, respectively, can give rise to lasing action in the visible region. From the visible emission spectra, yellow–blue (Y/B) intensity ratios and chromaticity color coordinates were also estimated. The lifetimes of ⁴F_9/2 metastable state for the samples with different concentrations were also measured and discussed.     

Optical properties of samarium doped zinc-phosphate glasses

Samarium doped zinc-phosphate glasses having composition Sm₂O_{3 (x)}ZnO_(60−x) P₂O_{5 (40)} (where x=0.1-0.5 mol%) were prepared by melt quenching method. The density of these glasses was measured by Archimedes method; the corresponding molar volumes have also been calculated. The values of density range from 3.34 to 3.87 gm/cm³ and those of molar volume range from 27.62 to 31.80 cm⁻³. The optical absorbance studies were carried out on these glasses to measure their energy band gaps. The absorption spectra of these glasses were recorded in UV-visible region. 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 of 2.89-4.20 eV. The refractive index and polarizability of oxide ion have been calculated by using Lorentz-Lorentz relations. The values of refractive index range from 2.13 to 2.42 and those of polarizability of oxide ion range from 6.51×10⁻²⁴ to 7.80×10⁻²⁴ cm³.     

Investigations on spectral features of tungsten ions in sodium lead alumino borate glass system

Na₂O–PbO–Al₂O₃–B₂O₃ (NPAB) glasses mixed with different concentrations of WO₃ (ranging from 0 to 2.5 mol%) are synthesized by conventional melt quenching method. The samples are characterized by X-ray diffraction (XRD), optical absorption, Electron paramagnetic resonance (EPR) and Fourier transform infrared (FT-IR) spectroscopic techniques. Glass formation is confirmed by X-ray diffraction spectra. The optical absorption spectra of these glasses exhibited a predominant broad band peak at about 850–870 nm is identified due to d_xy–d_x²_−y² transition of W⁵⁺ ions. From the optical absorption spectral data, optical band gap (E_opt) and Urbach energy (ΔE) are evaluated. From EPR spectra the strength of the signal is increased and hyperfine splitting is resolved with increasing concentration of WO₃ in the glass matrix. The FT-IR spectral studies have pointed out the existence of conventional BO₃, BO₄, B–O–B, PbO₄, WO₄ and WO₆ structural units of these glasses. Various physical properties and optical basicity are also evaluated with respect to the concentration of WO₃ ions.     

Europium doped strontium borate glasses and their optical properties

Optical absorption and luminescence spectra of europium doped strontium borate glasses prepared in different conditions are studied. It is found that the percentage of Eu³⁺ ions varies from 100 to 30% being controlled by the conditions of preparation. The mechanism, favoring reduction of europium to Eu²⁺ state in polycrystalline strontium tetraborate, is much weaker in glasses of the same composition. In samples containing mixed valence europium at densities of 8×10²⁰ cm⁻³, the efficient transfer of optical excitation from Eu³⁺ to Eu²⁺, suppressing the Eu³⁺ luminescence, has been found. The most reliable way of monitoring the percentage of europium ions in different valences for strontium borate glasses is the measuring of absorption at f-f transition ⁷F₀→⁵D₂ of Eu³⁺.     

Copper reduction and hydroxyl formation by hydrogen process in alumino-silicate glasses

The process of nanometric copper (Cu⁰) precipitation by hydrogen in alumino-silicate glasses was studied regarding the simultaneous formation of hydroxyl bonding. Firstly, copper-ion-doped alumino-silicate glasses were melt-quenched and then heat-treated in the presence of hydrogen gas, which allowed copper ions to be reduced into nanometric metal particles. Along with the metallic copper formation, there was also formed the hydroxyl groups as a byproduct of the reaction. From spectroscopic studies, it was revealed that the reduction process was kinetically controlled by the hydrogen diffusion into the glasses. After the Cu⁰ precipitation, in particular, at temperatures higher than 700 °C or for reduction times longer than 5 h the copper metal was found to move towards the surface, creating a copper metal rich surface. Moreover, an increase in hydrogen permeation with the treatment time was also observed and this tendency was more intense for the matrix, which allowed higher copper reduction.     

Effect of Bi2O3 on EPR, optical transmission and DC conductivity of vanadyl doped alkali bismuth borate glasses

Glasses with composition xBi₂O₃·(30−x)M₂O·70B₂O₃ (M=Li, Na) containing 2 mol% V₂O₅ have been prepared over the range 0≤x≤15 (x is in mol%). The electron paramagnetic resonance spectra of VO²⁺ of these glasses have been recorded in the X-band (≈9.3 GHz) at room temperature (RT≈300 K). Spin Hamiltonian parameters, g_∥, g_⊥, A_∥, A_⊥, dipolar hyperfine coupling parameter, P, and Fermi contact interaction parameter, K, have been calculated. The molecular orbital coefficients, α² and γ², have been calculated by recording the optical transmission spectra. In xBi₂O₃·(30−x)Li₂O·70B₂O₃ glasses there is decrease in the tetragonality of the V⁴⁺O₆ complex for x up to 6 mol% whereas for x≥6 mol%, tetragonality increases. In xBi₂O₃·(30−x)Na₂O·70B₂O₃ glasses there is increase in the tetragonality of the V⁴⁺O₆ complex with increasing x. The 3d_xy orbit expands with increase in Bi₂O₃:M₂O ratio. Values of the theoretical optical basicity, Λ_th, have also been reported. The DC conductivity increases with increase in temperature. The order of conductivity is 10⁻⁵ ohm⁻¹ m⁻¹ at low temperature and 10⁻³ ohm⁻¹ m⁻¹ at high temperature. The DC conductivity decreases and the activation energy increases with increase in Bi₂O₃:M₂O ratio.     

IR and Raman investigation on the structure of (100-x)B2O3-x[0.5 BaO-0.5 ZnO] glasses

Glasses with molar composition of (100-x)B₂O₃-x[0.5 BaO-0.5 ZnO], x=40, 50, 60, 70 were prepared from the melts of ZnO, BaCO₃ and H₃BO₃ mixture. The structure and thermal behavior were characterized by IR and Raman spectroscopy, DSC and Dilatometer. The investigation shows that the transition of the structural unit [BO₄] (B^IV) to [BO₃] (B^III) happens when BaO and ZnO content x increases in the borate glass, resulting in fewer B^III-O-B^IV bonds and more B^III-O-B^III bonds. At the same time, the diborate groups, which are found to be the predominant structural group of the glass with high B₂O₃ content, gradually changes into ring-type metaborate, pyro- and orthoborate groups. With increasing ZnO and BaO content x, the glass transition temperature (T_g) and the softening point (T_f) decreases, while linear expansion coefficient (α) increases, that comes from the weakening of the glass network.     

Compositional effects on the optical and thermal properties of sodium borophosphate glasses

A series of sodium borophosphate glasses of the composition (1−x)NaPO₃−xB₂O₃ have been synthesised from Na₂CO₃, B₂O₃ and P₂O₅ and their optical and thermal properties investigated. The results show that refractive index (n) and glass transition temperature (T_g) show a maximum at about B/(B+P)=0.6 while thermal expansion coefficient (α) and thermo-optic coefficient (dn/dT) change monotonically with the B/(B+P) ratio. These observations can be interpreted based on the incorporation of BO₃ and BO₄ units into the glass structural network.     

Synthesis, structure and magnetic properties of non-crystalline ferrihydrite nanoflakes

Synthesis and characterization of the structural and magnetic properties of a 2-line (2L) ferrihydrite (FHYD) sample based on the composition Fe:Al:Cu=100:25:5 are reported. Typical of 2L-FHYDs, this sample also yields the two broad lines in X-ray diffraction and triplet in the 1400-1700 cm⁻¹ range in IR spectroscopy. However, in transmission electron microscopy, nanoflakes of about 5-20 nm size but without any hint of diffraction fringes characteristic of crystalline order were observed. Temperature dependence (2-380 K) of the magnetization M vs. applied field H (up to ±65 kOe) of this non-crystalline ferrihydrite is used to establish a blocking temperature T_B?20 K, Néel temperature T_N?365 K and a spin-glass ordering of the surface Fe³⁺ spins at T_S?6 K. These magnitudes of T_B and T_S are considerably smaller than those of a 5 nm undoped 2L crystalline ferrihydrite with T_B=70 K and T_S=30 K. The fit of the M vs. H data for several T>T_B to a modified Langevin function is shown to collapse onto a universal curve yielding a temperature-independent average magnetic moment μ_P=70(5)μ_B per nanoflake. Analysis of these parameters obtained from the fits of M vs. H data above T_B is used to show that the effective average volume of the nanoflakes is about 1/3 that of spherical 5 nm crystalline 2L-FHYD. It is argued that these lower magnitudes of μ_P, T_B, and T_S for the nanoflakes result from their smaller effective volume determined here.     

EPR and optical absorption studies of Fe ions in sodium borophosphate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectral investigations have been carried out on Fe³⁺ ions doped sodium borophosphate glasses (NaH₂PO₄-B₂O₃-Fe₂O₃). The EPR spectra exhibit resonance signals with effective g values at g=2.02, g=4.2 and g=6.4. The resonance signal at g=4.2 is due to isolated Fe³⁺ ions in site with rhombic symmetry whereas the g=2.02 resonance is due to Fe³⁺ ions coupled by exchange interaction in a distorted octahedral environment. The EPR spectra at different temperatures (123-295 K) have also been studied. The intensity of the resonance signals decreases with increase in temperature whereas linewidth is found to be independent of temperature. The paramagnetic susceptibility (χ) was calculated from the EPR data at various temperatures and the Curie constant (C) and paramagnetic Curie temperature (θ_p) have been evaluated from the 1/χ versus T graph. The optical absorption spectrum exhibits bands characteristic of Fe³⁺ ions in octahedral symmetry. The crystal field parameter (Dq) and the Racah interelectronic repulsion parameters (B and C) have also been evaluated and discussed.     

Compositional dependence of the optical properties of novel Ge-Ga-Te-CsI far infrared transmitting chalcohalide glasses system

A systematic series of (Ge₁₅Ga₁₀Te₇₅)_1−x(CsI)_x (x=0, 5, 10, 15 at%) far infrared transmitting chalcohalide glasses were prepared by the traditional melt-quenching method. The physical, thermal and optical properties were determined. The allowed direct transition and indirect transition of samples were calculated according to the Tauc equation. The results show that glass transition temperatures (T_g) were in the range 133-175 °C, with ΔT values between 81 and 130 °C. The highest values of metallization criterion (0.244) and energy gap (1.191 eV) were obtained for (Ge₁₅Ga₁₀Te₇₅)₈₅(CsI)₁₅. When the dissolved amount of CsI increased from 0 to 15 at%, the direct optical band gap and indirect optical band gap were in the ranges 0.629-1.075 eV and 0.438-0.524 eV, respectively. The Ge-Ga-Te-CsI glasses have an effective transmission window between 1.7 and 25 μm, encompassing the region of interest for bio-sensing applications.     

Electron paramagnetic resonance, optical and electrical properties of vanadyl doped alkali germanoborate glasses

Glasses with composition xGeO₂.(0.30−x)M₂O.0.70B₂O₃ (M=Li, K) containing 2.0 mol% of V₂O₅ have been prepared in the range 0.00≤x≤0.15 by normal melt quenching method. Electron paramagnetic resonance (EPR), optical transmission and absorption spectra and dc conductivity of these glasses have been studied. Spin Hamiltonian parameters (SHPs) of VO²⁺ ions, dipolar hyperfine coupling parameter, P, Fermi contact interaction parameter, K and molecular orbital coefficients (α² and γ²) have been calculated. In GeO₂·Li₂O·B₂O₃ glasses there is no change in the tetragonality of the V⁴⁺O₆ complex and the size of 3d_xy orbit also remains unchanged with increase in GeO₂ content. In GeO₂·K₂O·B₂O₃ glasses, there is an increase in the tetragonality of the V⁴⁺O₆ complex and the 3d_xy orbit expands with increase in GeO₂ content. Values of the theoretical optical basicity, Λ_th, have also been reported. Optical band gap decreases with increase in GeO₂ content. The dc conductivity of these glasses decreases and the activation energy increases with increase in GeO₂:M₂O ratio.     

Micro Raman,Mossbauer and magnetic studies of manganese substituted zinc ferrite nanoparticles: Role of Mn

A series of Mn–Zn Ferrite nanoparticles (<15 nm) with formula Mn_xZn_1−xFe₂O₄ (where x=0.00, 0.35, 0.50, 0.65) were successfully prepared by citrate-gel method at low temperature (400 °C). X-ray diffraction analysis confirmed the formation of single cubic spinel phase in these nanoparticles. The FESEM and TEM micrographs revealed the nanoparticles to be nearly spherical in shape and of fairly uniform size. The fractions of Mn²⁺, Zn²⁺ and Fe³⁺ cations occupying tetrahedral sites along with Fe occupying octahedral sites within the unit cell of different ferrite samples are estimated by room temperature micro-Raman spectroscopy. Low temperature Mossbauer measurement on Mn_0.5Zn_0.5Fe₂O₄ has reconfirmed the mixed spinel phase of these nanoparticles. Room temperature magnetization studies (PPMS) of Mn substituted samples showed superparamagnetic behavior. Manganese substitution for Zn in the ferrite caused the magnetization to increase from 04 to18 emu/g and Lande's g factor (estimated from ferromagnetic resonance measurement) from 2.02 to 2.12 when x was increased up to 0.50. The FMR has shown that higher Mn cationic substitution leads to increase in dipolar interaction and decrease in super exchange interaction. Thermomagnetic (M–T) and magnetization (M–H) measurements have shown that the increase in Mn concentration (up to x=0.50) enhances the spin ordering temperature up to 150 K (blocking temperature). Magnetocrystalline anisotropy in the nanoparticles was established by Mossbauer, ferromagnetic resonance and thermomagnetic measurements. The optimized substitution of manganese for zinc improves the magnetic properties and makes these nanoparticles a potential candidate for their applications in microwave region and biomedical field.     

Superconducting gap in iron pnictides studied by optical spectroscopy

We investigated the in-plane optical spectrum of a Co-doped Ba(Fe_0.94Co_0.06)₂As₂ single crystal showing superconductivity below . In the normal state, the low-energy optical conductivity spectrum can be decomposed into a sharp Drude term and a broad “incoherent” term. Below T_c, an s-wave-like superconducting gap appears in both components. We also investigated a magnetic or spin-density-wave gap in the detwinned parent compound.     

Dielectric relaxation and a.c. conduction phenomena of PbO-PbF2-B2O3 glasses doped with FeO

PbO-PbF₂-B₂O₃ glasses containing different concentrations of FeO have been prepared. The glasses are characterized by X-ray diffraction and differential thermal analysis. The dielectric properties viz., dielectric constant, loss, conductivity, over a moderately wide range of frequency and temperature and dielectric breakdown strength have been investigated. The results of these studies have been analyzed in the light of different oxidation states of iron with the aid of the data on IR, ESR, optical absorption and magnetic susceptibility measurements. The analysis shows that iron ions exist mainly in Fe³⁺ state, occupy tetrahedral positions and increase the insulating strength of the glass if FeO is present in smaller concentrations. However, if FeO is present in higher concentrations in the glass matrix, (i) the dielectric relaxation intensity has been observed to increase, (ii) the intensity and the half width of the ESR signal has been observed to decrease and (iii) the value of magnetic moment (evaluated from magnetic susceptibility) has been observed to drop to a value of 4.6 μ_B from 5.7 μ_B. From these results it has been concluded that in this concentration range, iron ions exist mainly in divalent state.     

Doping effect of Mn on the magnetic behavior in Ni-Zn ferrite nanoparticles prepared by sol-gel auto-combustion

The ferrite samples of a chemical formula Ni_0.5−xMn_xZn_0.5Fe₂O₄ (where x=0.0, 0.1, 0.2, 0.3, 0.4, and 0.5) were synthesized by sol-gel auto-combustion method. The synthesized samples were annealed at 600 °C for 4 h. An analysis of X-ray diffraction patterns reveals the formation of single phase cubic spinel structure. The lattice parameter increases linearly with increase in Mn content x. An initial increase followed by a subsequent decrease in saturation magnetization with increase in Mn content is observed showing inverse trend of coercivity (H_c). Curie temperature decreases with increase in Mn content x. The initial permeability is observed to increase with increase in Mn content up to x=0.3 followed by a decrease, the maximum value being 362. Possible explanation for the observed structural, magnetic, and changes of permeability behavior with various Mn content are discussed.     

Studies on some alkali-phosphate glasses containing antimony and iron oxides

The effect of heat treatment on the Fe²⁺/Fe³⁺ ratio in some alkali phosphate glasses containing antimony and iron oxides has been investigated. Differential thermal analysis, Mossbauer spectroscopy, magnetic susceptibility and density measurements as well as the molar volume calculations were used in this study. The obtained data indicate that all glasses show approximately unchangeable stability. It is found, from the area under the Mossbauer absorption spectra that ferrous transformed gradually to ferric ions and the transformation rate constant was found to be 48 min⁻¹. The elapsed time was found to be 160 min. This transformation represents a first-order solid state reaction. The molar magnetic susceptibility measurements confirm the above results.