Role of MgO on the HAp forming ability in phosphate based glasses

Phosphate-based glasses 45P₂O₅–30CaO–(25 ? x)Na₂O–xMgO for different compositions of x = 0, 1, 2.5, 5 and 10 mol% were prepared using the normal melt quench technique. To study the influence of MgO on phosphate glasses, a series of experimental analyses such as ultrasonic velocities, differential thermal analysis, X-ray diffraction, energy-dispersive X-ray spectroscopy, pH measurements, Fourier transform infrared spectroscopy, scanning electron microscopy and in vitro studies were carried out in all the prepared glasses. A maxima in ultrasonic parameters at x = 2.5 mol% of MgO content and a further decrease in the same with the addition of MgO content were observed in all glasses. The observed results indicate that structural compactness of glass network took place up to 2.5 mol% of MgO (PCNM2.5), beyond which a loose packing of atoms led to structural softening in glass network. The results obtained from X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy analyses in all glasses before and after in vitro studies revealed the existence of higher HAp-forming ability in PCNM2.5 glass.     

Enhanced nonlinear optical and optical limiting properties of graphene/ZnO hybrid organic glasses

Graphene/ZnO (G/ZnO) composites were synthesized for the first time by a wet chemical method. X-ray diffraction and transmission electron microscopy analyses demonstrated that ZnO nanoparticles with an average diameter of about 5 nm uniformly covered the graphene surfaces. G/ZnO composites were dispersed in methyl methacrylate (MMA), polymerized at 75 °C for 30–35 min, and finally, dried at 45 °C for 10 h, to afford G/ZnO/PMMA organic glasses. UV–visible spectra showed that the band gaps of the G/ZnO/PMMA organic glasses were about 3.54 eV, larger than that of bulk ZnO because of the small size effect of ZnO nanoparticles. The nonlinear optical (NLO) and optical limiting (OL) properties of the G/ZnO/PMMA organic glasses were investigated by a modified Z-scan technique. The total NLO coefficient α₂ of the G/ZnO/PMMA organic glass was as high as 1530 cm/GW, which was approximately 5.6 and 7.8 times larger than those of G/PMMA and ZnO/PMMA organic glasses. The enhanced NLO properties of the G/ZnO/PMMA organic glasses led to excellent OL performance, which was attributed to the positive synergistic effects between graphene and ZnO.     

Dielectric dispersion and impedance spectroscopy of B3+-doped Ba(Ti0.9Sn0.1)O3 ceramics

In this study, the B₂O₃ doped Ba(Ti_0.9Sn_0.1)O₃ ceramics were prepared by using a solid state reaction method. Wide ranges of frequency (0.1 Hz to 1 MHz) and temperature (20–280 °C) dependence of the impedance relaxation were investigated. The impedance study indicates the presence of both dielectric relaxation in bulk and grain boundary effects in the material. The relaxation times for grain and grain boundary estimated from Cole–Cole plots varied with temperature according to the Arrhenius relation. The activation energy for grain and grain boundary were estimated to be 0.73 and 0.85 eV, respectively.     

Structural,thermal, dielectric and ac conductivity properties of lithium fluoro-borate optical glasses

Transparent and stable glasses in the chemical composition of Li₂O–LiF–B₂O₃–MO (M = Zn and Cd) have been prepared by a conventional melt quenching method. For these glasses, absorption spectra, structural (XRD, FT-IR, and Raman spectra), thermal (TG–DTA and DSC), dielectric (?′, ?″, tan δ), ac conductivity (σ_ac), and electric modulus (M′ and M″) have been investigated. Amorphous nature of these glasses has been confirmed from their XRD profiles. The LFB glasses with the presence of ZnO or CdO an extended UV-transmission ability has been achieved. The measured FT-IR and Raman spectra have exhibited the vibrational bands of B–O from [BO₃] and [BO₄] units and Li–O. The dielectric properties (tan δ, dielectric constant (?′), dielectric loss (?″)), electrical modulus and electrical conductivity (σ_ac) of these glasses have also been studied from 100 Hz to 1 MHz at the room temperature. Based on the trends noticed in the ac conductivities, the present glasses could be found useful as battery cathode materials.     

Impedance and modulus spectroscopy characterization of lead free barium titanate ferroelectric ceramics

In this work, dense BaTiO₃ ceramics were successfully prepared by the solid state reaction process. X-ray diffraction technique showed single-phase polycrystalline sample with perovskite structure. Dielectric behavior and the impedance relaxation were investigated in a wide range of temperature (room temperature (RT) – 40 °C) and frequency (1 kHz–1 MHz). A broad dielectric constant peak was observed over a wide temperature range around the phase transition temperature. The complex impedance plot exhibited two impedance semicircles identified over the frequency range of 1 kHz–1 MHz, which is explained by the grain and grain boundary effects. The presence of non-Debye type of relaxation has been confirmed by the complex impedance analysis. The centers of the impedance semicircles lie below the real axis, which indicates that the impedance response is a Cole–Cole type relaxation.     

Impedance spectroscopic behaviour of spark plasma sintered nanocrystalline scandia stabilized zirconia (SSZ)

Nanocrystalline scandia (Sc₂O₃) doped zirconia was prepared by dissolution and co-precipitation method. The formation of the nanostructured nearly cubic phase has been observed from transmission electron microscope and X-ray diffraction studies. Spark plasma sintering retains the nano/submicrograin structure. The frequency dependent conductivities were measured in the frequency range from 100 Hz to 1 MHz and at temperatures 300–800 K. The impedance diagram shows the grain interior and grain boundary resistance contributions. The frequency dependent conductance spectra show the DC plateau (at low frequency region) and dispersive region suggesting the correlated hopping motion of ions. The dielectric-loss spectra suggest the presence dielectric relaxation, which is related to enthalpy of ion hopping. Characteristic hopping frequencies were calculated and appear to be related to the thermally activated ion hoping process.     

High-quality c-axis oriented non-vacuum Er doped ZnO thin films

Preparation, growth, structure and optical properties of high-quality c-axis oriented non-vacuum Er doped ZnO thin films were studied. Zn_1−xEr_xO (x=0.0, 0.01, 0.02, 0.04, and 0.05) precursor solutions were prepared by sol–gel synthesis using Zn, and Er based alkoxide which were dissolved into solvent and chelating agent. Zn_1−xEr_xO thin films with different Er doping concentration were grown on glass substrate using sol–gel dip coating. Thin films were annealed at 600 °C for 30 min, and tried to observe the effect of doping ratio on structural and optical properties. The particle size, crystal structure, surface morphologies and microstructure of all samples were characterized by X-Ray diffraction (XRD) and Scanning Electron Microscope (SEM). The UV–vis spectrometer measurements were carried out for the optical characterizations. The surface morphology of the Zn_1−xEr_xO films depend on substrate nature and sol–gel parameters such as withdrawal speed, drying, heat treatment, deep number (film thickness) and annealing condition. Surface morphologies of Er doped ZnO thin films were dense, without porosity, uniform, crack and pinhole free. XRD results showed that, all Er doped ZnO thin films have a hexagonal structure and (002) orientation. The optical transmittance of rare earth element (Er) doped ZnO thin films were increased. The Er doped ZnO thin films showed high transparency (>85) in the visible region (400–700 nm).     

Optical properties of Yb-doped ZnO/MgO nanocomposites

Yb³⁺ doped ZnO/MgO nanocomposite were prepared by combustion synthesis method. The samples were further heated to 1000 °C to improve their crystallinity and photoluminescent efficiency. The concentrations of Yb³⁺ and Mg²⁺ were varied between 1–2% and 5–70% respectively in prepared samples. The nano-powders were characterized by Scanning Electron Microscopy and X-ray Diffraction for morphology and structural determination. XRD studies have revealed the wurtzite structure for Mg_xZn_1−xO for Mg concentrations below 30%. Higher concentrations of Mg results in Yb³⁺ doped ZnO/MgO nanocomposite containing three phases; the wurzite hexagonal phase typical of ZnO, the cubic phase of MgO and a small amount of cubic Yb₂O₃ phase. As expected, the amount of cubic phase in nano-powders increased with the increase of Mg concentration in ZnO. The crystallite size of ZnO/MgO composites decreased from 55 nm to 30 nm with increase of Mg content. SEM images of Yb³⁺ doped ZnO/MgO nanocomposite with higher Mg content (>50%) showed clearly distinct hexagonal and cubical shaped nano-particles. Photoluminescent emission showed a broad band in the range (435 nm to 700 nm). Pure ZnO nano-phosphor showed an emission peak around 545 nm, which is blue shifted with Mg content. The photoluminescence intensity increased with increase of Mg content in ZnO and it became maximum with 30% Mg concentration. Time resolved decay curves of photoluminescence indicated decay time in microsecond time scale.     

Effects of glass additions on the microstructure and dielectric properties of barium strontium titanate (BST) ceramics

Commercial glass frits (lead borosilicate glasses) were employed as the sintering aids to reduce the sintering temperatures of BST ceramics. The effects of the glass content and the sintering temperature on the microstructures, dielectric properties and tunabilities of BST ceramics have been investigated. Densification of BST ceramics of 5 wt% glass content becomes significant from sintering temperature of 1000 °C. The glass content shows a strong influence on the Curie temperature T_c, permittivity and the diffuse transition. X-ray results show all BST ceramics exhibit a perovskite structure and also the formation of a secondary phase, Ba₂TiSi₂O₈. The shift of BST diffraction peaks towards higher angle with increasing the glass content indicates the substitution of Pb²⁺ in Ba²⁺ site, which mainly accounts for the diffuse transition observed in these BST ceramics. BST ceramics with 10 wt% glass additives possess the highest tunability at all four sintering temperatures. A tunability of 12.2% at a bias field of 1 kV/mm was achieved for BST ceramics with 10 wt% glass content sintered at 900 °C.     

Structure and optical properties of transparent Er3+-doped CaF2–silica glass ceramic prepared by controllable sol–gel method

Transparent Er³⁺-doped CaF₂–silica glass ceramics were prepared by the direct physical introduction of Er³⁺ doped CaF₂ nanocrystals into acid-catalyzed sol–gel silica glass. The physical methods of ball milling, ultrasonic baths, and stirring were investigated to disperse Er³⁺ doped CaF₂ nanocrystals in the silica sols. The CaF₂–silica sol mixture went through gelation and heat-treatment to form Er³⁺-doped CaF₂–silica glass ceramics. The morphology of Er³⁺ doped CaF₂ in silica glass did not change after heat-treatment at 600 °C for 10 h. The experimental results showed that Er³⁺ doped CaF₂ in the glass ceramic prepared with the assistance of ball milling possesses the best dispersity and homogeneity. The highest in-line transmittance of the glass ceramic reached up to 85% in visible region. Glass ceramic exhibits efficient up-conversion emissions corresponding to the Er³⁺:⁴F_9/2→⁴I_15/2 transition and long lifetime of ⁴F_9/2 level (1.73 ms) under 980 nm excitation.     

The changes in structural and optical properties of (ZnO:AlN) thin films fabricated at different RF powers of ZnO target

AlN doped ZnO thin films were prepared on glass and Si (100) substrates by RF sputtering. The ratio of nitrogen (N₂) to Argon (Ar) used to prepare the films was 80:20. The films were deposited at different RF powers of 150 W, 175 W, 200 W, 225 W and 250 W for ZnO target and 200 W for AlN target. XRD results revealed the existence of (002) ZnO phase for RF power of ZnO target above 175 W. However, at the RF power of 150 W, the film exhibited amorphous properties. The prepared films showed transmission values above 70% in the visible range. The average calculated value of energy band gap and the refractive index were 3.43 eV and 2.29 respectively. The green and UV emission peaks were observed from PL spectra. Raman Peaks at 275.49 cm^?1 and 580.17 cm^?1 corresponding to ZnO:N and ZnO:AlN were also observed.     

Effects of Ag additive on structure and crystallization behaviors of As2(Se15Te85)3 glasses

In this work, glass samples of compositions of As_40-0.4x(Se₁₅Te₈₅)_60-0.6xAg_x (x = 0, 10, 16.7, 20, 25 at%) are prepared. The structural transformations of glasses are deduced from the variations of glass densities and Raman spectra with the addition of Ag. Differential scanning calorimetry is applied to determine the characteristic temperatures, evaluate the thermal stabilities against crystallization, and investigate the crystallization kinetics under non-isothermal conditions. Thermal treatment of the as-prepared glass samples is carried out at both low (190 °C) and high (260 °C) crystallization temperatures. X-ray diffraction patterns demonstrate that crystals precipitated from glass matrices are pure As-Te(Se) phases free of Ag. The results are consistent with the Raman spectra. The relevant mechanism can be understood based on the dual chemical role of the Ag addition on the variations of glass network.     

Preparation and properties of Ge–Ga–La–S–AgI chalcogenide glass

Chalcogenide glasses of 65GeS₂–(25–x)Ga₂S₃–10AgI–xLa₂S₃ (x=0, 1, 3, and 5 mol%) were fabricated through the traditional melt-quenching method. The effects of addition of La₂S₃ on physical, thermal and optical properties of the glass system were investigated. The results showed that the fabricated glasses possess considerably high glass transition temperature, exhibit improved mechanical property and excellent infrared transmission. A redshift at the visible absorbing cut-off edge is observed with increasing of La₂S₃ content. The direct and indirect optical band gap values are also calculated. Raman spectra analysis indicated that the band at 265 cm⁻¹ decreased in amplitude and a new peak at 230 cm⁻¹ was detected manifesting the formation of La-S bond in the network. In addition, the mid-infrared emission at 3.74 µm of the glasses doped with Tm³⁺ ions was achieved. The results indicated that the glasses are promising materials for mid-infrared applications such as imaging, remote sensing and lasers.     

Structural characterization of TiO2–P2O5–CaO glasses by spectroscopy

The structure of glasses with composition x TiO₂·(65 ? x) P₂O₅·35 CaO (x = 0–30 mol%) has been studied and their glass transition temperature, Raman and NMR spectra have been analysed.For TiO₂-free glass two phosphate species have been identified as Q² and Q³. Increasing TiO₂ content in glass compositions results in the disappearance of the Q³ and Q² species and in the formation of, mainly, pyrophosphate structure, Q¹.In calcium titanophosphate glass with higher TiO₂ content the structure consists of a distorted Ti octahedral linked to pyrophosphate unit through P–O–Ti bonds. In these glass series the structural cohesion increases with TiO₂, although a depolymerization in the original P–O–P network occurs.The study of these glasses and the understanding of their structural characteristics can give a valuable contribution for the clarification of their degradation behaviour namely in biological environments.     

Photoluminescence, γ-irradiation and X-ray induced luminescence studies of Sm3+-doped oxyfluorosilicate glasses and glass-ceramics

Sm³⁺-doped oxyfluorosilicate glasses were fabricated through traditional melt quenching technique. After the heat treatment of the prepared glass, transparent SrF₂ nanocrystalline glass-ceramics (GC) were obtained. The amorphous nature of the prepared glasses and crystalline phase (SrF₂) of the GC were confirmed by XRD analysis. Abbe number was calculated for all the prepared glasses by measuring refractive index at different wavelengths. In the framework of Judd-Ofelt (JO) theory, the JO intensity parameters were obtained from the absorption spectra of 1.0 mol% Sm₂O₃-doped glass. The photoluminescence spectrum was recorded with 401 nm excitation. From the analysis of optical spectra and JO parameters, the radiative properties like radiative transition probabilities, branching ratios and radiative lifetimes for the fluorescent levels of Sm³⁺ ions were determined. The effect of γ-irradiation on luminescence properties and X-ray induced luminescence properties were also studied. The emission intensity was increased for GC where as it decreases with increase of γ-irradiation dosages. There are no noticeable changes in the position as well as intensity in photoluminescence and X-ray induced luminescence spectra for GC sample but after the γ-irradiation, the emission intensity was decreased moderately. The luminescence decay profiles for ⁴G_5/2 level were recorded and it is changed from exponential to non-exponential nature for higher Sm³⁺ ion concentrations. The decay profiles which exhibit non-exponential nature are well fitted to the Inokuti-Hirayama model and determined the energy transfer parameters. By using the integrating sphere, the quantum yield values were obtained for all the prepared glasses. The detailed study of the present glasses reveals that these glasses could be useful for radiation shielding and scintillation applications.     

Low temperature firing of Co2Y–NiCuZn ferrite composites

Hexagonal structure magnetoplumbite ferrites have revealed a higher dispersion frequency than that of nickel ferrites because of the magnetoplumbite's magnetic anisotropy. The magnetoplumbite ferrite densification temperature always exceeds 1000 °C and the initial low temperature firing permeability of magnetoplumbite ferrites with added glass is too low (μ_i = 2–4). Therefore, it is desirable to develop a material that has a higher permeability at above 300 MHz and can be densified at temperatures below 900 °C. The Bi₂O₃–B₂O₃–ZnO–SiO₂ (BBSZ) glass addition effects on the densification and magnetic properties of Co₂Y–NiCuZn ferrite composites with various Co₂Y/NiCuZn ferrite ratios were investigated. The densification of Co₂Y–NiCuZn ferrite composites was enhanced by the addition of glass at low sintering temperatures (<900 °C) due to the liquid phase sintering. Co₂Y–NiCuZn ferrite composites with 4 wt% BBSZ glass sintered at 900 °C show a relative density above 90%, a high-initial-permeability of 5–6, a quality factor of above 30 in the 200–300 MHz frequency and a resonance frequency above 1 GHz, which can be used in high frequency multilayer chip inductors.     

Synthesis and characterization of Bi1.5Zn0.92Nb1.5−xSnxO6.92−x/2 pyrochlore ceramics

The morphological, compositional, structural, dielectric and electrical properties of Bi_1.5Zn_0.92Nb_1.5?xSn_xO_6.92?x/2 ceramics have been investigated by means of scanning electron microscopy (SEM), X-ray energy dispersion spectroscopy (EDS), X-ray diffraction (XRD), temperature and frequency dependent dielectric constant and temperature dependent conductivity measurements for Sn-contents in the range of 0.00 ≤ x ≤ 0.60. It was shown that single phase of the pyrochlore ceramics can only be obtained for x ≤ 0.25. Above this value a ZnO phase appeared in the XRD patterns and SEM micrographs as well. An increase in the lattice constant and in the temperature coefficient of dielectric constant and a decrease in the dielectric constant values with increasing Sn content was observed for the ceramics which exhibited a single phase formation. A temperature dependent but frequency invariant dielectric constant was observed for this type of ceramics. The lowest electrical conductivity and highest dielectric constant was observed for the sample which contains 0.06 Sn. The Bi_1.5Zn_0.92Nb_1.5?xSn_xO_6.92?x/2 pyrochlore ceramic conductivities are thermally active above 395 K. For temperatures greater than 395 K, the conductivity activation energy which was found to be 0.415 eV for the pure sample increased to 1.371 eV when sample was doped with 0.06 Sn.     

Preparation by solar physical vapor deposition (SPVD) and nanostructural study of pure and Bi doped ZnO nanopowders

Pure and Bi doped ZnO nanopowders have been prepared by a physical vapor deposition process in a solar reactor (SPVD). From X-ray diffraction (XRD) spectra performed on initial targets and on the nanopowders obtained, the lattice parameters and the phase changes as well as the average grain sizes and the grain shape anisotropies have been determined. High Resolution Transmission Electron Microscopy (HRTEM) observations support the results. The pure ZnO nanopowders “grain size” and “grain shape anisotropy” (whiskers with an average diameter of 20–40 nm) is a function of the air pressure during the vaporisation–condensation process: the higher the pressure, the longer the whiskers. The bismuth doped ZnO nanopowders are polyphased but the ZnO based majority phases behave similarly to pure ZnO with a tendency to form whiskers but with a grain size and grain shape anisotropy decreasing when the Bi content increases.Preliminary electrical measurements at temperatures below 300 °C have shown that the ionic conductivity of the nanocomposites obtained starting from ZnO + 23 wt% Bi₂O₃ targets is high and promising for applications.     

Enhancement of up-conversion emission and emerging cool white light emission in co-doped Yb3+/ Er3+: Li2O-LiF-B2O3-ZnO glasses for photonic applications

A series of co-doped (Yb³⁺/Er³⁺): Li₂O-LiF-B₂O₃-ZnO glasses were prepared by standard melt quenching technique. Structural and morphological studies were carried out by XRD and FESEM. Phonon energy dynamics have been clearly elucidated by Laser Raman analysis. The pertinent absorption bands were observed in optical absorption spectra of singly doped and co-doped Yb³⁺/Er³⁺: LBZ glasses. We have been observed a strong up-conversion red emission pertaining to Er³⁺ ions at 1.0 mol% under the excitation of 980 nm. However, the up-conversion and down conversion (1.53 µm) emission intensities were remarkably enhanced with the addition of Yb³⁺ ions to Er³⁺: LBZ glasses due to energy transfer from Yb³⁺ to Er³⁺. Up-conversion emission spectra of co-doped (Yb³⁺/Er³⁺): LBZ glasses exhibits three strong emissions at 480 nm, 541 nm and 610 nm which are assigned with corresponding electronic transitions of ²H_9/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 respectively. Consequently, the green to red ratio values (G/R) also supports the strong up-conversion emission. The Commission International de E′clairage coordinates and correlated color temperatures (CCT) were calculated from their up-conversion emission spectra of co-doped (Yb³⁺/Er³⁺): LBZ glasses. The obtained chromaticity coordinates for optimized glass (0.332, 0.337) with CCT value at 5520 K are very close to the standard white colorimetric point in cool white region. These results could be suggested that the obtained co-doped (Yb³⁺/Er³⁺): LBZ glasses are promising candidates for w-LEDs applications.     

The effect of zinc substitution on the magnetism of magnesium ferrite nanostructures crystallized from borate glasses

Glasses in the system 51.7 B₂O₃/9.3 K₂O/1 P₂O₅/10.4 Fe₂O₃/(27.6–x) MgO/ x ZnO (with x=0, 5, 10, 13.8 and 20 mol%) were prepared by the conventional melt quenching method. The as prepared glass samples were thermally treated at 560 °C for 3 or 6 h. The effect of substituting MgO by ZnO in the glass network on the crystallized phase was studied. The resulting magnetic glass ceramics were characterized using X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and transmission electron microscopy (TEM) including energy dispersive X-ray analysis (EDX). The substitution of Mg by Zn resulted in a larger lattice parameter of the precipitated crystals, while the crystallite size does not change significantly. TEM micrographs, recorded from extracted particles, showed the formation of small aggregates with about 30 nm in diameter. These agglomerates contain crystals with sizes in the range from 7 to 9 nm. EDX measurements proved the incorporation of Zn²⁺ ions into the crystal phase. Room temperature magnetic measurements of the samples with up to 10 mol% ZnO showed hysteresis loops which are characteristic for super paramagnetic (SPM) behavior. A magnetic contribution was not detected for samples with higher ZnO concentrations. The maximum magnetization varied with the composition of the glass ceramics to a great extent.