Structural and physical characteristics of Au2O3-doped sodium antimonate glasses – Part II electrical characteristics

In continuation of our earlier investigations on structural and physical characteristics of Au₂O₃-doped sodium antimonate glass-ceramics (Part-1), in this part we have investigated the influence of gold ions on electrical characteristics of the Na₂O–Sb₂O₃: Au₂O₃ glass-ceramics. The study contains the results of quantitate investigations on dielectric properties, impedance spectra and A.C. conductivity in larger ranges of continuous frequencies (4 Hz-8 MHz) and temperatures (300-630 K). The variations exhibited by dielectric parameters with temperature and also with frequency were discussed in terms of various polarization mechanisms. The observed dielectric relaxation effects were analyzed using pseudo Cole-Cole plot method and the analysis indicated spreading of relaxation times for dipoles. A.c. conductivity and also d.c. conductivity were found to decrease (to three orders of magnitude) with increase in Au₂O₃ concentration upto 0.1 mol%. The decrement is ascribed to the increasing concentration of Sb⁵⁺ ions that were predicted to participate in the glass network forming with SbO₄ units. Even though, both ionic and polaronic contributions are possible for conduction in the studied material, quantitative analysis of these results indicated that the polaronic conduction (due to intervalence transfer between Sb³⁺ ↔ Sb⁵⁺ and Au⁰ ↔ Au³⁺) is prevalent. The results have also suggested that there is a gradual decrement in the ionic component with increase in Au₂O₃ concentration. Variation in σ_ac in the low-temperature region could satisfactorily be explained using quantum mechanical tunneling (QMT) model. Analysis of the results of d.c. conductivity indicated that the small polaron hoping (SPH) model is valid, especially in a high-temperature region while the low temperature part of d.c. conductivity is analyzed based on variable range hopping (VRH) model. Overall, the increase in Au₂O₃ dopant concentration in the studied glass-ceramics caused a decrement in the magnitude of the conductivity or increase in the insulating strength of the material.     

Structural,luminescence and NMR studies on Nd3+-doped sodium–calcium-borate glasses for lasing applications

In this work, Neodymium (Nd³⁺) -doped borate glasses were synthesised by melt-quenching method and their structural as well as optical properties were analysed through XRD, Raman, NMR, DSC, UV–Visible, luminescence and decay studies for the possible application as laser gain medium. DSC and XRD results revealed that the glasses have high transition temperature and are in amorphous nature, respectively. The vibrational characteristics of the host matrices as well as the effect of Nd³⁺ incorporation were analysed by using Raman spectra, which exhibit majorly borate groups as supported by NMR results. The band gap energy of the glasses decreases with an increase in Nd³⁺ concentration. Using Judd-Oflet theory the characteristic intensity parameters (Ω_λ, λ = 2, 4 and 6) were calculated and further used for calculating the various radiative parameters from the emission spectra. The emission cross-section (σ_em) was estimated as high as 1.15 × 10⁻²⁰ cm² from the Füchtbauer–Landenburg (FL) equation for the dominant ⁴F_3/2→⁴I_11/2 (1056 nm) transition. The effect of Nd³⁺ concentration on the lifetime of the ⁴F_3/2 luminescent level was analysed from the decay curve analyses. From which, the corresponding quantum efficiency (η) was estimated and found as high as 54%. The investigated result suggests the prepared glasses can be utilized as gain medium to generate laser at around 1.05 μm.     

Radiation response properties of Eu3+-doped K2O–Ta2O5–Ga2O3 glasses

Eu₂O₃-doped 40K₂O–20Ta₂O₅–40Ga₂O₃ gallate glasses were synthesized, and their radiation response characteristics were studied systematically. According to their photoluminescence spectra, they showed intense emissions with sharp peaks centered at around 580, 594, 613, 656, and 706 nm when irradiated by 380 nm light. The sharp peaks originate from the 4f-4f transitions of Eu³⁺. Moreover, these sharp peaks were also detected when excited by X-ray, and the 1.0% Eu₂O₃-doped gallate glasses showed the largest luminescence intensity under UV light and X-ray. Furthermore, the afterglow levels of the Eu₂O₃-doped 40K₂O–20Ta₂O₅–40Ga₂O₃ gallate glasses were determined to be approximately 300 ppm. These levels are close to the levels of TI-doped CsI single crystals.     

Calcium aluminate cement tapes – Part I: Structural and microstructural characterizations

This present paper concerns the structural and microstructural characterization of 1 mm thick calcium aluminate cement tapes prepared by tape casting. A study of the effect of environment, time and the consolidation temperature on the structural properties and microstructure has been undertaken. Consolidation environments studied are air, water and an environment saturated in humidity for storage durations of 1, 4 or 30 days at a temperature of 20 or 70 °C. The structural characterization was carried out using XRD. The microstructural characterization was carried out through the distribution of pore volume by mercury porosimetry measurements and SEM micrographs. The effects of the various consolidation parameters were compared and discussed. The tape consolidated for 30 days in water at 70 °C has the most advanced hydration with the formation of stable hydrates. This is evidenced by the reduction of the inter-granular pore size and the microstructure densification.     

Synthesis,physical, optical,mechanical, and radiation attenuation properties of TiO2–Na2O–Bi2O3–B2O3 glasses

A series of bismo-borate (50-x)B₂O₃-xTiO₂-15Na₂O–30Bi₂O₃ glass samples (where x = 0, 2.5, 5, 7.5, and 10 wt%) doped with TiO₂ were fabricated via the melt-quenching technique. The gamma and neutron shielding, physical, optical, and mechanical properties of the prepared samples were investigated. The experimental results were measured using an HPGe detector. ¹⁵²Eu, ¹³³Ba, ¹³⁷Cs, and ⁶⁰Co radioactive sources were used with energies in the range of 81–1408 keV. The experimental results were compared with both the FLUKA code and the XCOM database. The addition of TiO₂ increased the density of the glass samples and decreased their molar volume. The mass attenuation coefficient (MAC) decreased as photon energy decreased, while it increased as TiO₂ concentration increased. The half value layer (HVL) and mean free path (MFP) of the glass samples increased when the photon energy increased and decreased as the TiO2 concentration increased. The absorbance of the present samples is enhanced by using TiO₂, meaning they can be used to protect humans from UV light. Both direct and indirect band gaps decreased as TiO₂ content increased from 0 to 10 wt %. Moreover, the electronic transition between localized states is valid in the present samples. The radiation shielding, optical, physical, and mechanical properties of the fabricated glass samples demonstrate their utility for diagnostic gamma shielding.     

Effects of TeO2/B2O3 substitution on synthesis,physical, optical and radiation shielding properties of ZnO–Li2O-GeO2-Bi2O3 glasses

Tellurite glass is a model material having superior features for several applications. It can be considered as a potential host matrix for different oxides, and this paper aims to study the effects of TeO₂/B₂O₃ substitution on synthesis, physical, optical and radiation shielding properties of ZnO–Li₂O-GeO₂-Bi₂O₃ glasses produced by melt quenching technique. The physical and optical features of the fabricated glasses were experimentally investigated by determining pivotal parameters such as density, XRD, tellurium ion concentration (N_i), linear refractive index (n_o), polaron radius (r_p) and inter nuclear distance (r_i). Moreover, the relative radiation deposition within the glasses was assessed via the attenuation coefficients (e.g. MAC), specific gamma ray constant (ᴦ), total stopping power (TSP), neutron cross sections, and dose rate (D). Our results suggest that both TeO₂ and B₂O₃ additives have a significant effect on the fundamental properties of the ZnO–Li₂O-GeO₂-Bi₂O₃ glasses. It also found that the lower thicknesses of the present glasses are required to provide the same level of shielding than ordinary, ilmenite, steel scrap, hematic-serpentine, ilmenite-limonite and basalt-magnetite concretes, RS253-G18 and RS360 glass shields. Therefore, presently investigated glasses are promising photon shields in different technological applications of gamma- and x-rays.     

Oxide ion/electronic polarizability,optical basicity and linear dielectric susceptibility of TeO2 – B2O3 – SiO2 glasses

A system of bio-silica borotellurite glasses was fabricated based on the chemical formula [(TeO₂)_0.7 (B₂O₃)_0.3]_1-x (SiO₂)_x with x = 0.1, 0.2, 0.3, and 0.4 using the melt-quenching technique using silica (98.548% SiO₂, from rice husk), TeO₂ (Alfar Aeser, 99.9%) and B₂O₃ (Alfar Aeser, 99.9%). Measurements and characterizations such as density and molar volume measurements, XRD analysis, FTIR, and UV–Vis spectroscopes were performed on the studied glasses. The objective was to determine the glasses’ applicability in optoelectronics, non-linear optics, and laser technologies through polarizability, linear electric susceptibility, and optical basicity study. Apart from confirming the amorphous nature of the glasses, the XRD analysis identified the presence of a crystalline phase of tellurium oxide (α-TeO₂) formed. The FTIR spectral study revealed the presence of TeO₃, BO₃, and SiO₄ structural units in the studied glasses. The refractive index (2.3026 – 2.2651), molar polarizability (8.0696 – 9.4334 Å³), oxide ion polarizability (3.2970 – 3.6202 Å³), electronic polarizability (0.2296 – 0.2335 Å³), dielectric constant (5.1307 – 5.3019), optical basicity (0.6719 – 0.7998), metallization criterion (0.410853 – 0.420714) and electric susceptibility (0.3286 – 0.3422 esu) of the glasses were presented. With the high refractive index and favourable electronic/oxide ion polarizability as well as good electric susceptibility, the glasses have shown great potential for optical fibre and laser applications. Metallization criterion value falls in the range of glasses with great potentials for non-linear optical application. The dielectric value suggests the glasses represent wideband semiconducting glasses believed to be good for application in microelectronic substrates fabrication.     

Structural and electrical characteristics of high-κ Er2O3 and Er2TiO5 gate dielectrics for a-IGZO thin-film transistors

In this letter, we investigated the structural and electrical characteristics of high-κ Er₂O₃ and Er₂TiO₅ gate dielectrics on the amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film transistor (TFT) devices. Compared with the Er₂O₃ dielectric, the a-IGZO TFT device incorporating an Er₂TiO₅ gate dielectric exhibited a low threshold voltage of 0.39 V, a high field-effect mobility of 8.8 cm²/Vs, a small subthreshold swing of 143 mV/decade, and a high I_on/I_off current ratio of 4.23 × 10⁷, presumably because of the reduction in the oxygen vacancies and the formation of the smooth surface roughness as a result of the incorporation of Ti into the Er₂TiO₅ film. Furthermore, the reliability of voltage stress can be improved using an Er₂TiO₅ gate dielectric.     

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.     

Thermal and devitrification behavior of CaO–Ga2O3–SiO2 glasses

A study of the influence of the substitution of Ga₂O₃ for CaO, at constant O/Si ratio, on thermal properties and non-isothermal devitrification of 2.5CaO.2SiO₂ is reported. Differential thermal analysis (DTA) and X-ray diffraction analysis were used. The X-ray diffraction pattern of the crystallized Ga₂O₃ base glass shows that the αCaO SiO₂, that should be stable only above 1125°C, forms in the temperature range 900–1000°C. A new ternary crystalline phase, whose reflections are not reported in the JCPDS cards, was found to form during crystallization of the glass. The glass transformation temperature, T_g, and softening, T_s, temperature decrease as Ga₂O₃ is substituted for CaO. This is the result of the substitution of the network modifying cation Ca²⁺, of higher coordination number, by a network forming cation Ga³⁺ in fourfold coordination, in a composition range of relative insensitivity to changes of covalent cross-linking density. The crystal growth activation energy, E_c, decreases with substitution; this is the consequence of the decrease of the structural rigidity and of the shift of crystallization to a higher temperature range. Devitrification involves a mechanism of surface nucleation; surface nuclei behaving as bulk nuclei in samples that soften and sinter before devitryfing.     

Structural and thermal characterization of CaO–MgO–SiO2–P2O5–CaF2 glasses

The influence of varying the CaO/MgO ratio on the structure and thermal properties of CaO–MgO–SiO₂–P₂O₅–CaF₂ glasses was studied in a series of eight glass compositions in the glass forming region of diopside (CaMgSi₂O₆)–fluorapatite [Ca₅(PO₄)₃F]–wollastonite (CaSiO₃) ternary system. The melt-quenched glasses were characterized for their structure by infrared spectroscopy (FTIR) and magic angle spinning (MAS)-nuclear magnetic resonance (NMR) spectroscopy. Silicon is predominantly present as Q² (Si) species, while phosphorus tends to coordinate in orthophosphate environment. The sintering and crystallization parameters of the glasses were obtained from differential thermal analysis (DTA) while crystalline phase fractions in the sintered glass–ceramics were analyzed by X-ray diffraction adjoined with Rietveld refinement. Diopside, fluorapatite, wollastonite and pseudowollastonite crystallized as the main crystalline phases in all the glass–ceramics with their content varying with respect to variation in CaO/MgO ratio in glasses. The implications of structure and sintering behaviour of glasses on their bioactivity were discussed.     

Structural characterization,energy transfer,and Judd–Ofelt analysis of pure and the Eu3+-doped Ca2LiMg2V3O12 phosphors

A novel vanadate host Ca₂LiMg₂V₃O₁₂ (CLMV) and the Eu³⁺-doped samples were synthesized via a solid-state reaction method. The phase formation and the morphological analysis were studied in detail. The Rietveld refinement result shows that the host belongs to cubic space group Ia-3d (230) with lattice parameter, a = 12.3948 Å, V = 1904.23 Å³, and Z = 8. The diffuse reflectance spectroscopy measurement estimated the bandgap of the host and the CLMV:0.05Eu³⁺ phosphors. The host exhibits a broad absorption band (peak at 345 nm) ranging from 240 to 380 nm, which is attributed to the charge transfer in the O²⁻–V⁵⁺ complex. Under near UV excitation (λ_exc = 345 nm), the host gives a broad emission band covering the visible region from 400 to 730 nm and the emission is in the bluish–green region of the CIE diagram. When the host is doped with the Eu³⁺ ions and excited at 345 nm, the emission spectrum depicts the superimposition of the characteristic emission bands (red emission) of the Eu³⁺ ions corresponding to the f–f transitions over the broad emission band of the host. The calculated color coordinates (9600 to 2280 K) demonstrated the color tuning ability of the phosphor as the dopant concentration is increased in the host. This is because the VO₄³⁻ group plays the sensitiser role and partially transfers energy with the Eu³⁺ ions. When the same set of phosphors were excited at the dominant characteristic excitation band (λ_exc = 394 nm) of the Eu³⁺, the characteristic emission bands of the Eu³⁺ in the orange–red region were observed. As the electric dipole transition of the Eu³⁺ was found to be dominant, the prepared phosphors possessed high color purity (CP). The energy transfer mechanism and the lifetime values were also presented. The temperature-dependent PL studies showed good thermal stability of the optimum sample. Various radiative transition properties were analyzed by the Judd–Ofelt theory. The photometric results reveal the color tuning ability and CP of the CLMV:xEu³⁺ phosphors.     

The characteristics of ZnO–Bi2O3-based varistor ceramics doped with Y2O3 and varying amounts of Sb2O3

ZnO–Bi₂O₃-based varistor samples doped with 0.45 mol% of Y₂O₃ and varying amounts of Sb₂O₃ in the range from 1.8 to 0.0 mol% were fired at 1230 °C. Only in the samples co-doped with Sb₂O₃ did doping with Y₂O₃ resulted in the formation of a fine-grained Bi–Zn–Sb–Y–O phase (the Y₂O₃-containing phase) at the grain boundaries, which very effectively hinders the grain growth. Despite of a decrease in the amount of added Sb₂O₃ from 1.8 to 0.45 mol% and a significant decrease in the amount of spinel phase the samples had a similar ZnO grain size and a threshold voltage of 200 V/mm. The results confirmed that doping with Y₂O₃ is a very promising route for the production of fine-grained high-voltage ZnO–Bi₂O₃-based varistor ceramics, and determining the proper amounts of added Sb₂O₃ and Y₂O₃ is of great importance.     

Effect of Al2O3 and K2O content on structure,properties and devitrification of glasses in the Li2O–SiO2 system

The effect of Al₂O₃ and K₂O content on structure, sintering and devitrification behaviour of glasses in the Li₂O–SiO₂ system along with the properties of the resultant glass–ceramics (GCs) was investigated. Glasses containing Al₂O₃ and K₂O and featuring SiO₂/Li₂O molar ratios (3.13–4.88) far beyond that of lithium disilicate (Li₂Si₂O₅) stoichiometry were produced by conventional melt-quenching technique along with a bicomponent glass with a composition 23Li₂O–77SiO₂ (mol.%) (L₂₃S₇₇). The GCs were produced through two different methods: (a) nucleation and crystallization of monolithic bulk glass, (b) sintering and crystallization of glass powder compacts.Scanning electron microscopy (SEM) examination of as cast non-annealed monolithic glasses revealed precipitation of nanosize droplet phase in glassy matrices suggesting the occurrence of phase separation in all investigated compositions. The extent of segregation, as judged from the mean droplet diameter and the packing density of droplet phase, decreased with increasing Al₂O₃ and K₂O content in the glasses. The crystallization of glasses richer in Al₂O₃ and K₂O was dominated by surface nucleation leading to crystallization of lithium metasilicate (Li₂SiO₃) within the temperature range of 550–900 °C. On the other hand, the glass with lowest amount of Al₂O₃ and K₂O and glass L₂₃S₇₇ were prone to volume nucleation and crystallization, resulting in formation of Li₂Si₂O₅ within the temperature interval of 650–800 °C.Sintering and crystallization behaviour of glass powders was followed by hot stage microscopy (HSM) and differential thermal analysis (DTA), respectively. GCs from composition L₂₃S₇₇ demonstrated high fragility along with low flexural strength and density. The addition of Al₂O₃ and K₂O to Li₂O–SiO₂ system resulted in improved densification and mechanical strength.     

Plasticization of Fibrous Cellulose Acetate: Part I – Synthesis and Characterization

Synthesis and characterization of fibrous cellulose triacetate, CTA, are reported using an acetic acid/anhydride/perchloric acid toluene catalyzed route. The fibrous product exhibits a high degree of nano-crystallinity. An optimum concentration of the reactants for substitution and minimization of fiber degradation was studied. Chain degradation was promoted by the acetylium ion and led to a loss of fibrous structure. Heterogeneity of the material was studied by powder X-ray diffraction, optical microscopy, and solid-state ¹³C nuclear magnetic resonance. The structure formed if directly influenced by the original nano structure in the cellulose fiber.     

Synthesis and Properties of Fusion-Cast Refractories in the Al2O3 – B2O3 System

Synthesis and properties of fusion-cast high-alumina refractories in the Al₂O₃ – B₂O₃ system are reported. Adding B₂O₃ is shown to improve density and fabricability of the fusion-cast products. As shown by x-ray diffractometry and petrographic analysis, the phase composition of synthetic products is represented by corundum and 9Al₂O₃ 2B₂O₃ boroaluminate. Corrosion tests in molten industrial glasses have shown the potential use of these materials in the melting technology of VS-92-grade optical lead silicate glass.