Optical absorption and thermoluminescence studies on LiF-Sb2O3-B2O3 glasses doped with Ni ions

20LiF-(30−x)Sb₂O₃-50B₂O₃:xNiO glasses with the value of x (ranging from 0 to 1.0 mol% in steps of 0.2) were prepared. A number of studies, viz. differential scanning calorimetry, optical absorption, magnetic susceptibility and thermoluminescence, on these glasses were carried out as a function of nickel ion concentration. An anomaly has been observed in all the properties of these glasses when NiO concentration is about 0.6 mol%. The results of these studies were analysed in the light of different environments of nickel ions in the glass network.     

Dielectric dispersion in PbO-Sb2O3-As2O3:V2O5 glasses

Dielectric properties, viz. dielectric constant ε′, loss tan δ and a.c conductivity σ_ac (over a wide range of frequency and temperature) and dielectric breakdown strength of PbO-Sb₂O₃-As₂O₃ glasses doped with V₂O₅ (ranging from 0 to 0.5 mol%) are studied. Analysis of these results, based on optical absorption and ESR spectra, indicates that the insulating strength of the glasses is comparatively high when the concentration of V₂O₅ is about 0.3 mol% in the glass matrix.     

Nickel ion—A structural probe in BaO-Al2O3-P2O5 glass system by means of dielectric, spectroscopic and magnetic studies

BaO-Al₂O₃-P₂O₅ glasses containing different concentrations of NiO (ranging from 0 to 1.0 mol%) were prepared. A number of studies viz., chemical durability, differential thermal analysis, spectroscopic (infrared, optical absorption spectra), magnetic susceptibility and dielectric properties (constant ε′, loss tan δ, AC conductivity σ_AC over a range of frequency and temperature) of these glasses have been carried out. The studies on chemical durability indicate that there is a significant increase in the corrosion resistance of the glasses; where as the results of differential thermal analysis suggests that there is a substantial improvement in the glass forming ability, with increase in the concentration of NiO up to 0.6 mol% in the glass matrix. The optical absorption, magnetic susceptibility and IR spectral studies point out nickel ions occupy both tetrahedral and octahedral positions in the glass network; the later positions seems to be dominant when the concentration of NiO is beyond 0.6 mol% in the glass matrix. The studies of dielectric properties reveal that the presence of nickel oxide in the glass network causes a considerable improvement in the insulating strength of the se glasses when the concentration of NiO?0.6 mol%.     

Influence of valence states and co-ordination of cobalt ions on dielectric properties of PbO-Bi2O3-As2O3:CoO glass system

The glasses of the composition (40−x) PbO-15Bi₂O₃-45As₂O₃-xCoO, with 0≤x≤0.6 mol% in the steps of 0.1 were synthesized. The dielectric properties viz., dielectric constant, loss and ac conductivity over moderately larger ranges of frequency and temperature were investigated. The results were analyzed with the aid of the data on optical absorption and IR spectra. The analysis indicated that there is an increase in the insulating strength of the glasses with increase in the concentration of CoO up to 0.4 mol%.     

Spectroscopic and magnetic studies of manganese ions in ZnO-Sb2O3-B2O3 glass system

ZnO-Sb₂O₃-B₂O₃ glasses containing different concentrations of MnO ranging from 0 to 1.0 mol% were prepared. A number of studies, viz. optical absorption, infrared and ESR spectra and magnetic susceptibility, were carried out as a function of manganese ion concentration. The analysis of the results indicate that manganese ions mostly exist in Mn²⁺ state in these glasses when the concentration of MnO≤0.6 mol% and above this concentration, these ions seem to exist in Mn³⁺ state in the glass network.     

The role of As2O3 on the stability and some physical properties of PbO-Sb2O3 glasses

PbO-Sb₂O₃ glasses added with different concentrations of As₂O₃ (10-55 mol%) were prepared to understand their IR spectra, elastic properties (Young's modulus E, Shear modulus G, microhardness H), optical absorption and dielectric properties (constant ε, loss tan δ, ac conductivity σ_ac over a moderately wide range of frequency and temperature and breakdown strength in air medium at room temperature). Results have indicated that the structure of the PbO-Sb₂O₃-As₂O₃ glass is more rigid when the concentration of As₂O₃ is around 40 mol%.     

Study on the influence of TiO2 on the insulating strength of ZnO-ZnF2-B2O3 glasses by means of dielectric properties

ZnO-ZnF₂-B₂O₃ glasses containing small concentrations of TiO₂ ranging from 0 to 0.6 mol% were prepared. Dielectric properties (constant ε′, loss tan δ, ac conductivity σ_ac over a moderately wide range of frequency and temperature at room temperature in air medium) of these glasses have been studied. The results of these studies were analyzed with the aid of data on optical absorption, ESR and IR spectra of these glasses. The analysis suggests that when the concentration of TiO₂>0.2 mol%, the titanium ions, in addition to Ti⁴⁺ state, co-exist in Ti³⁺ state, act as modifiers and reduce the breakdown strength.     

Study on dielectric and magnetic properties of Ho3Fe5O12 ceramics

Ho₃Fe₅O₁₂ ceramics with garnet structure were prepared by the solid-state reaction method. The results revealed the existence of Fe²⁺ ions have intensive influence on dielectric and magnetic properties of Ho₃Fe₅O₁₂ ceramics, which could be further confirmed by oxygen treatment. With a magnetic field lower than 10 kOe, the ME coefficient reaches 33 ps m⁻¹ at room temperature. And the ME coupling was further verified by dielectric anomaly near Néel temperature.     

Physical studies on composites Ag7I4VO4-Al2O3

The electrical properties of the solid electrolytes Ag₇I₄VO₄-Al₂O₃ (0-40 mol% Al₂O₃) are investigated. The electrical conductivity, dielectric constant and dielectric loss are increased by increasing the concentration of Al₂O₃; showing a maximum at 30 mol% Al₂O₃. The conductivity is found to be increased by decreasing the particle size of Al₂O₃. The results are explained using the random resistor network model (RRN). This is due to the formation of a highly conducting interface layer along the matrix-particle interface. This layer is destroyed at concentrations higher than 30 mol% Al₂O₃.     

EPR and magnetic susceptibility studies of iron ions in ZnO-Fe2O3-SiO2-CaO-P2O5-Na2O glasses

Room temperature electron paramagnetic resonance (EPR) spectra and temperature dependent magnetic susceptibility data have been obtained on bulk x(ZnO,Fe₂O₃)(65−x)SiO₂20(CaO, P₂O₅)15Na₂O (6≤x≤21 mole%) glasses prepared by melt quenching method. EPR spectra of the glasses revealed absorptions centered at g≈2.1 and 4.3. The variations of the intensity and line width of these absorption lines with composition have been interpreted in terms of the variation in the concentration of the Fe²⁺ and Fe³⁺ ions in the glass and the interaction between the iron ions. EPR and magnetic susceptibility data of the glasses reveal that both Fe²⁺ and Fe³⁺ ions are present in the glasses, with their relative concentration being dependent on the glass composition. The studies reveal superexchange type interactions in these glasses, which are strongly dependent on their iron content.     

Glass formation in the Sb2O3-ZnBr2 binary system

Glass formation has been investigated in the Sb₂O₃-ZnBr₂ binary system. Vitreous samples have been obtained for batches containing 20-90 mol% Sb₂O₃. Chemical analysis shows that bromine concentration is smaller than expected and real compositions belong to the Sb₂O₃-ZnBr₂-ZnO ternary system. However, the discrepancy between nominal and analyzed compositions is fair for Sb₂O₃ content larger than 50 mol%. Optical transmission lies between 400 nm and 7 μm and refractive index ranges from 2.0 to 2.1. Glass transition occurs around 300 °C, and crystallization exotherm does not appear in the differential scanning calorimetry scan at 10 K s⁻¹ for samples containing 50-60 mol% Sb₂O₃. Thermal expansion varies between 120 and 220×10⁻⁷ K⁻¹ as antimony content decreases. Microhardness is close to 200 kg/mm². These glasses have low phonon energy and make potential materials for infrared transmission and active fibers.     

Synthesis and laser patterning of Bi-doped Y3Fe5O12 crystals in germanosilicate glasses

New germanosilicate glasses giving the crystallization of yttrium iron garnet Y₃Fe₅O₁₂ (YIG) and Bi-doped YIG, 23Na₂O-xBi₂O₃-(12−x)Y₂O₃-25Fe₂O₃-20SiO₂-20GeO₂ (mol%), are developed, and the laser-induced crystallization technique is applied to the glasses to pattern YIG and Bi-doped YIG crystals on the glass surface. It is clarified from the Mössbauer effect measurements that iron ions in the glasses are present mainly as Fe³⁺. It is suggested from the X-ray diffraction analyses and magnetization measurements that Si⁴⁺ ions are incorporated into YIG crystals formed in the crystallization of glasses. The irradiations (laser power: 32-60 mW and laser scanning speed: 7 μm/s) of continuous wave Yb:YVO₄ fiber laser (wavelength: 1080 nm) are found to induce YIG and Bi-doped YIG crystals, indicating that Fe³⁺ ions in the glasses act as suitable transition metal ions for the laser-induced crystallization. It is suggested that YIG and Bi-doped YIG crystals in the laser irradiated part might orient. The present study will be a first step for the patterning of magnetic crystals containing iron ions in glasses.     

Role of Al2O3 in upconversion and NIR emission in Tm and Er codoped calcium fluoro phosphorous silicate glass system

In this study, the principal role of Al₂O₃ on the features of the photoluminescence spectra of Tm³⁺ ion and upconversion phenomenon in Tm³⁺ and Er³⁺ codoped CaF₂−Al₂O₃−P₂O₅−SiO₂ glass system has been investigated. The concentration of Al₂O₃ is varied from 2 to 10 mol% while that of Er³⁺ and Tm³⁺ is fixed. IR and Raman spectral studies have indicated that there is a gradual increase in the degree of disorder in the glass network with increase in the concentration of Al₂O₃ up to 6.0 mol%. This is attributed to the presence of Al³⁺ ions in octahedral positions in larger proportions. When the glasses are doped with Tm³⁺ ions, the blue and red emissions were observed, whereas in Er³⁺ doped glasses blue, green and red emissions were observed. When the glasses are codoped with Tm³⁺ and Er³⁺ ions and excited at 790 nm, all the three emission lines were observed to be reinforced, especially in the glasses mixed with 6.0 mol% of Al₂O₃. The IR emission band detected at about 1.8 μm due to ³F₄→³H₆ transition of Tm³⁺ ions is also observed to be strengthened due to codoping. The reasons for enhancement in the intensity of various emission bands due to codoping have been identified and discussed with the help of rate equations for various emission transitions.     

Ag concentration dependent transport properties of LiF-MoO3-P2O5 glasses

LiF-MoO₃-P₂O₅ glasses mixed with different concentrations of Ag₂O (ranging from 0 to 1.0 mol%) was prepared. D.C. conductivity and dielectric properties over a range of temperature have been investigated. The analysis of the results of d.c. conductivity has indicated that T>θ_D/2, the small polaron hoping model seems to be fit and the conduction is adiabatic in nature. These results further indicated that there is a change over of conduction mechanism from electronic to ionic at about 0.4 mol% of Ag₂O. The low temperature part of a.c. conductivity is explained based on quantum mechanical tunneling model. The quantitative analysis of these results is further extended with the aid of the data on optical absorption, ESR and IR spectral studies.     

Magnetoelectric characterization of xNi0.75Co0.25Fe2O4-(1−x)BiFeO3 nanocomposites

Magnetoelectric (ME) nanocomposites containing Ni_0.75Co_0.25Fe₂O₄-BiFeO₃ phases were prepared by citrate sol-gel process. X-ray diffraction (XRD) analysis showed phase formation of xNi_0.75Co_0.25Fe₂O₄-(1−x)BiFeO₃ (x=0.1, 0.2, 0.3 and 0.4) composites on heating at 700 °C. Transmission electron microscopy revealed the formation of powders of nano order size and the crystal size was found to vary from 30 to 85 nm. Dispersion in dielectric constant (ε) and dielectric loss (tan δ) in the low-frequency range have been observed. It is seen that nanocomposites exhibit strong magnetic properties and a large ME effect. On increasing Ni_0.75Co_0.25Fe₂O₄ contents in the nanocomposites, the saturation magnetization (M_S) and coercivity (H_C) increased after annealing at 700 °C. The large ME output in the nanocomposites exhibits strong dependence on magnetic bias and magnetic field frequency. The large value of ME output can be attributed to small grain size of ferrite phase of nanocomposite being prepared by citrate precursor process.     

Features of the local structural disorder in Li2O-CaF2-P2O5 glass-ceramics with Cr2O3 as nucleating agent

Li₂O-CaF₂-P₂O₅ glasses mixed with different concentrations of Cr₂O₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy (EDS), differential thermal analysis and conventional spectroscopic techniques. The X-ray diffraction and scanning electron microscopic studies reveal the presence of lithium phosphate, calcium phosphate and chromium phosphate (complexes of Cr³⁺, Cr⁵⁺ and Cr⁶⁺ ions) crystal phases. The study on DTA suggests that the crystallization is predominantly due to the surface crystallization when the concentration of nucleating agent Cr₂O₃ is around 0.8 mol%. The IR and Raman spectral studies of these samples indicate that the sample crystallized with 0.8 mol% Cr₂O₃ is more compact and possesses high rigidity due to the presence of chromium ions largely in tetrahedral positions.     

Magnetism and thermal induced characteristics of Fe2O3 content bioceramics

Magnetic properties of Li₂O–MnO₂–CaO–P₂O₅–SiO₂ (LMCPS) glasses doped with various amounts of Fe₂O₃ were investigated. There is a dramatic change in the magnetic property of pristine LMCPS after the addition of Fe₂O₃ and crystallized at 850 °C for 4 h. Both the electron paramagnetic resonance and magnetic susceptibility measurements showed that the glass ceramic with 4 at% Fe₂O₃ exhibited the coexistence of superparamagnetism and ferromagnetism at room temperature. When the Fe₂O₃ content was higher than 8 at%, the LMCPS glasses showed ferromagnetism behavior. The complex magnetic behavior is due to the distribution of (Li, Mn)ferrite particle sizes driven by the Fe₂O₃ content. The thermal induced hysteresis loss of the crystallized LMCPS glass ceramics was characterized under an alternating magnetic field. The energy dissipations of the crystallized LMCPS glass ceramics were determined by the concentration and Mn/Fe ratios of Li(Mn, Fe)ferrite phase formed in the glass ceramics.     

Bioactivity of SiO2-CaO-P2O5-Na2O glasses containing zinc-iron oxide

Glasses with composition x(ZnO,Fe₂O₃)(65 − x)SiO₂20(CaO,P₂O₅)15Na₂O (6 ≤ x ≤ 21 mol%) were prepared by melt-quenching technique. Bioactivity of the glasses was investigated in vitro by examining apatite formation on the surface of glasses treated in acellular simulated body fluid (SBF) with ion concentrations nearly equal to those in human blood plasma. Formation of bioactive apatite layer on the samples treated in SBF was confirmed by using Fourier transform infrared reflection (FTIR) spectroscopy, grazing incidence X-ray diffraction (GI-XRD) and scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer. Development of an apatite structure on the surface of the SBF treated glass samples as functions of composition and time could be established using the GI-XRD data. FTIR spectra of the glasses treated in SBF show features at characteristic vibration frequencies of apatite after 1-day of immersion in SBF. SEM observations revealed that the spherical particles formed on the glass surface were made of calcium and phosphorus with the Ca/P molar ratio being close to 1.67, corresponding to the value in crystalline apatite. Increase in bioactivity with increasing zinc-iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of glass composition and immersion time in SBF.     

Luminescence spectroscopy of Ti ions in Li2O-CaF2-P2O5 glass ceramics

Li₂O-CaF₂-P₂O₅ glasses mixed with different concentrations of TiO₂ (ranging from 0 to 0.8 mol%) were crystallized at 500 °C. The photo luminescence spectra of these samples excited with the wavelengths corresponding to their absorption edges have been recorded at room temperature. The spectra exhibited an emission band in the wavelength region 470-500 nm. The emission band is identified due to the charge transfer from O²⁻ ion in to empty 3d orbital of octahedrally positioned Ti⁴⁺ ions. The analysis of the results further indicates the highest luminescence efficiency for the glass ceramic sample crystallized with 0.6 mol% of TiO₂.     

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.