Highly stable persistent spectral hole burning in Eu ions doped oxy-fluoride glasses of 30CaF2–10Al2O3–60B2O3

High temperature persistent spectral hole burning up to room temperature has been observed in Eu³⁺ ions doped oxy-fluoride glasses with a composition of 30CaF₂–10Al₂O₃–60B₂O₃ (mol%) melted in a reducing atmosphere. The hole stability was studied through light-induced hole refilling and temperature cycling experiments. The burned holes survive thermal cycling to 300 K due to a high barrier height of 0.69 eV in the sample.     

Electrical properties of glasses in the Na2O–MoO3–P2O5 system

A range of coloured electronic or mixed ionic–electronic glasses has been evidenced in the Na₂O–MoO₃–P₂O₅ system. The properties of these glasses have been studied along different composition lines corresponding either to a fixed Na₂O content or a constant Mo/P ratio. An EPR spectroscopy investigation of these glasses has allowed to determine the Mo⁵⁺ ion percentages in these materials. The electrical properties of these glasses have been studied by impedance spectroscopy, and the electronic and ionic contributions have been evaluated. The properties of these sodium glasses have been compared with those of lithium glasses with the same compositions.     

Low-temperature ionic conductivity of the solid solution in the system ZrO2–Y2O3–Yb2O3

Compositional dependence of ionic conductivity in the system ZrO₂–Y₂O₃–Yb₂O₃ was investigated in the temperature range 573–873 K using the complex impedance technique. It was shown that the conductivity decreases with increasing concentration of Yb₂O₃ in the system ZrO₂–Y₂O₃–Yb₂O₃. Analyzing the experimental data according to the classic Arrhenius equation showed that such an experimental phenomenon can be attributed to the tighter association between Yb³⁺ and oxygen vacancy, compared with that between Y³⁺ and oxygen vacancy, which hinders the migration of oxygen vacancy in the materials.     

Glass formation and conductivity in the Pb2P2O7–Ag4P2O7–AgI system

A large glass-forming domain has been identified in the Pb₂P₂O₇–Ag₄P₂O₇–AgI system. The physical properties have been determined as a function of AgI content. The ionic conductivity has been studied as a function of the Ag⁺ ion total concentration and the Ag⁺ ion concentration issued from the AgI component. The structure and electrical properties of obtained glasses are compared with those of ionic glasses of the Ag₄P₂O₇–AgI system.     

Comparison of the electrochemical behavior of CeO2–SnO2 and CeO2–TiO2 electrodes produced by the Pechini method

CeO₂–SnO₂ and CeO₂–TiO₂ thin films were prepared by the Pechini method and their characteristics were compared, using a fractional factorial design to quantify the effect of five preparation variables. It was observed that CeO₂–SnO₂ electrodes show a greater electrochemical response than the CeO₂–TiO₂ films. The best intercalation charge densities were 18.11 and 9.91 mC/cm² for CeO₂–SnO₂ and CeO₂–TiO₂, respectively. Both films were optically inactive with transparencies, in most cases, higher than 90%.     

Structural and optical properties of (100 − x)(Li2B4O7) − x(SrO–Bi2O3–0.7Nb2O5–0.3V2O5) glasses and glass nanocrystal composites

Glasses of various compositions in the system (100 − x)(Li₂B₄O₇) − x(SrO–Bi₂O₃–0.7Nb₂O₅–0.3V₂O₅) (10  x  60, in molar ratio) were prepared by splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as-quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X-ray powder diffraction studies. Glass composites comprising strontium bismuth niobate doped with vanadium (SrBi₂(Nb_0.7V_0.3)₂O_9−δ (SBVN)) nanocrystallites were obtained by controlled heat-treatment of the as-quenched glasses at 783 K for 6 h. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat-treated at 783 K/6 h) confirm the presence of rod shaped crystallites of SBVN embedded in Li₂B₄O₇ glass matrix. The optical transmission spectra of these glasses and glass nanocrystal composites of various compositions were recorded in the wavelength range 190–900 nm. Various optical parameters such as optical band gap (E_opt), Urbach energy (ΔE), refractive index (n), optical dielectric constant and ratio of carrier concentration to the effective mass (N/m^*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied.     

Corrosion of magnesia–chrome brick in molten MgO–Al2O3–SiO2–CaO–FetO slag

The corrosion of magnesia–chrome (MgO–Cr₂O₃) brick in molten MgO–Al₂O₃–SiO₂–CaO–Fe_tO slag has been characterized using a dynamic rotary slag corrosion testing for various test cycles at 1650 °C. The open porosity decreases from 15.3 to 4.0% for three cycles, then it gradually increases from 4.0 to 4.8% when the test is extended to nine cycles, in which the permeating depth of the slag maintains at about 20 mm. The XRD pattern of the permeated layer shows the presence of the MgO, MgCr₂O₄ and CaMgSiO₄ phases. In the interior of the permeating layer cracks are formed and corrosion starts at the pores and cracks of MgO and decreases gradually. However, at 20–40 mm beneath the permeated layer edge, different shapes of MgO particles are found.     

Preparation and optical properties of sol–gel derived Er-doped Al2O3–Ta2O5 films

Thin films of the system xAl₂O₃–(100 − x)Ta₂O₅–1Er₂O₃ were prepared by a sol–gel method and a dip-coating technique. The influences of the composition and the crystallization of the films on Er³⁺ optical properties were investigated. Results of X-ray diffraction indicated that the crystallization temperature of Ta₂O₅ increased from 800 to 1000 °C with increased values of x. In crystallized films, the intensities of the visible fluorescence and upconversion fluorescence tend to decrease with an increase in x values, due to the high phonon energy of Al₂O₃; the strongest fluorescence is observed in a crystallized film for x = 4 heat treated at 1000 °C. In amorphous films obtained by heat treatment at relatively low temperatures the Er³⁺ fluorescence could not be observed because strong fluorescence from organic residues remaining in the films thoroughly covered the Er³⁺ fluorescence. On the other hand, the Er³⁺ upconversion fluorescence in the amorphous films was observed to be stronger than that in the crystallized films. The strongest upconversion fluorescence is observed in an amorphous film for x = 75 heat treated at 800 °C.     

Preparation and properties of radiofrequency sputtered X-ray amorphous films in the system SiO2–ZrO2

Amorphous films in the system SiO₂–ZrO₂ were prepared by radiofrequency sputtering method and their density, refractive index, elastic constants, and thermal expansion coefficient were measured. All of the physical properties had a similar compositional dependence; that is, they increased, but not proportionally, with increasing ZrO₂ content. The coordination states of cations in these amorphous films were estimated by the compositional dependence of volume and molar refractivity. The coordination state of silicon ions in the amorphous films did not change, but the coordination number of zirconium ions changed from 8 to 6, depending on ZrO₂ content. These results indicate that, in amorphous films in the system SiO₂–ZrO₂, the change of the coordination state of zirconium ions in the amorphous films has an important effect on the properties.     

Effect of preparation conditions on properties of atomic layer deposited TiO2 films in Mo–TiO2–Al stacks

TiO₂ films were grown by atomic layer deposition on Mo electrodes in order to elucidate the dominating conductance mechanism and its dependence on the growth chemistry. TiCl₄ and Ti(OC₂H₅)₄ served as titanium precursors, and H₂O or H₂O₂ as oxygen precursors. The films grown at lower temperatures were amorphous. With increasing growth temperatures the crystallization first started in the TiCl₄–H₂O process. The films grown in this process were clearly leakier compared to the films grown from Ti(OC₂H₅)₄ and H₂O and from Ti(OC₂H₅)₄ and H₂O₂. In the Ti(OC₂H₅)₄-based processes, the application of H₂O₂ instead of H₂O resulted in the films with considerably lowered conductivity, although structural differences in these films were insignificant. Space–charge-limited currents were prevailing in all our amorphous Mo–TiO₂–Al packages. Measurements at different temperatures suggested quite high trap densities likely due to the presence of impurities and structural disorder, while the strong differences in conductivity seemed to be due to different densities of gap states.     

Sensitivity enhancement for H2 gas detection using a SnO2–Ag2O–PdOx nanocrystalline system

Thick film H₂ sensors were fabricated using SnO₂ loaded with Ag₂O and PdO_x. The composition that gave highest sensitivity for H₂ was in the wt.% ratio of SnO₂:Ag₂O:PdO_x as 93:5:2. The nano-crystalline powders of SnO₂–Ag₂O–PdO_x composites synthesized by sol–gel method were screen printed on alumina substrates. Fabricated sensors were tested against gases like H₂, CH₄, C₃H₈, C₂H₅OH and SO₂. The composite material was found sensitive against H₂ at the working temperature 125 °C, with minor interference of other gases. H₂ gas as low as 100 ppm can be detected by the present fabricated sensors. It was found that the sensors based on SnO₂–Ag₂O–PdO_x nanocrystalline system exhibited high performance, high selectivity and very short response time to H₂ at ppm level. These characteristics make the sensor to be a promising candidate for detecting low concentrations of H₂.     

Third order nonlinear optical characterization of new chalcohalogenide glasses containing lead iodine

The vitreous formation in a new chalcohalogenide system based on As, Sb, Bi, S, Pb and I has been studied. Wide vitreous regions have been identified both in the ternary As₂S₃–Sb₂S₃–PbI₂ system and in the quaternary As₂S₃–Sb₂S₃–Bi₂S₃–PbI₂ system. More particularly, in the latter case, the vitreous regions have been investigated and established for the two layers of the system corresponding respectively to 10% and 20% molar of Bi₂S₃. Due to the richness of these new glasses in highly polarizable elements, they are of interest for the implementation of high nonlinear optical properties. To explore the potentialities of chalcogenide glasses for ultra-fast optical applications, the nonlinear refractive indices (real and imaginary part) of different compositions are measured. Nonlinear measurements have been performed through a pump/probe experiment using a Mach-Zehnder interferometer coupled to a CCD camera. The measured values are as high as 16×10⁻¹⁸ m²/W for the nonlinear refractive index and 6 cm/GW for the nonlinear absorption.     

Microstructures, densification and mechanical properties of TiC–Al2O3–Al composite by field-activated combustion synthesis

Dense TiC–Al₂O₃–Al composite was prepared with Al, C and TiO₂ powders by means of electric field-activated combustion synthesis and infiltration of the molten metal (here Al) into the synthesized TiC–Al₂O₃ ceramic. An external electric field can effectively improve the adiabatic combustion temperature of the reactive system and overcome the thermodynamic limitation of reaction with x < 10 mol. Thereby, it can induce a self-sustaining combustion synthesis process. During the formation of Al₂O₃–TiC–Al composite, Al is molten first, and reacted with TiO₂ to form Al₂O₃, followed by the formation of TiC through the reaction between the displaced Ti and C. Highly dense TiC–Al₂O₃–Al with relative density of up to 92.5% was directly fabricated with the application of a 14 mol excess Al content and a 25 V cm⁻¹ field strength, in which TiC and Al₂O₃ particles possess fine-structured sizes of 0.2–1.0 μm, with uniform distribution in metal Al. The hardness, bending strength and fracture toughness of the synthesized TiC–Al₂O₃–Al composite are 56.5 GPa, 531 MPa and 10.96 MPa m^1/2, respectively.     

Optical band gap studies on xPb3O4–(1−x)P2O5 lead[(II, IV)] phosphate glasses

A series of glasses in the xPb₃O₄–(1−x)P₂O₅ (red lead phosphate) (RLP) system with ‘x' varying from 0.075 to 0.4 were prepared by the single-step melt quenching process from Pb₃O₄ and NH₄H₂PO₄. The optical absorption spectra of these glasses have been recorded in the ultraviolet region from 200 to 400 nm and the fundamental absorption edges have been identified. The optical band gap E_opt values have been determined for all the glasses using the known theories. The (E_opt) values vary from 4.90 to 3.21 eV the highest being 4.57 eV, corresponding to the most stable glass of x=0.225. The absorption edge is attributed to the indirect transitions and the origin of the Urbach energy ΔE is suggested to be thermal vibrations. These glasses promise as potential candidates for application in optical technology compared to simple xPbO–(1−x)P₂O₅ (lead phosphate) (LP) glasses.     

Stark level analysis for Er-doped ZBLAN glass

From the absorption and emission spectra recorded in a conventional way at 13 K, the Stark levels in manifolds from ⁴I_15/2 to ²H_9/2 for Er³⁺-doped ZBLAN (ZrF₄–BaF₂–LaF₃–AlF₃–NaF) glass have been investigated by means of the effective crystal field model previously proposed to describe the average of local symmetries occupied by rare earth ions in oxide glasses [1]. This model, based on the principle of descending symmetry, used the symmetry group chain scheme. Crystal field strength, homogeneous and inhomogeneous widths of levels have been determined, and the former models and results about optical properties for rare earth ions in heavy metal fluoride glasses are discussed. In fluoride glasses, the rare earth ions appear more evenly distributed than in oxide glasses, and the crystal field strength is weaker than in oxide glasses.     

Synthesis of MoSi2–Al2O3 nanocomposite by mechanical alloying

MoSi₂–Al₂O₃ nanocomposite was synthesized by mechanical alloying (MA) of MoO₃, SiO₂ and Al powder mixture. The structural evolution of the powders was studied by X-ray diffraction (XRD). Both β-MoSi₂ and -MoSi₂ were obtained after 3 h of milling. The spontaneous formation of β-MoSi₂ during milling proceeded by a mechanically induced self propagating reaction (MSR), analogous to that of the self propagating high temperature synthesis (SHS). After 70 h of milling the β-phase transformed to -phase. The crystallite size of -MoSi₂ and Al₂O₃ after milling for 100 h was 12 and 17 nm, respectively. Residual Mo and Si in the 3 and 70 h milled samples formed β-MoSi₂ and Mo₅Si₃ during heating at 1000 °C, respectively.     

Frequency dependent electrical conductivity and dielectric relaxation behavior in amorphous (90V2O5–10Bi2O3) oxide semiconductors doped with SrTiO3

We report on the experimental results of frequency dependent a.c. conductivity and dielectric constant of SrTiO₃ doped 90V₂O₅–10Bi₂O₃ semiconducting oxide glasses for wide ranges of frequency (500–10⁴ Hz) and temperature (80–400 K). These glasses show very large dielectric constants (10²–10⁴) compared with that of the pure base glass (≈10²) without SrTiO₃ and exhibit Debye-type dielectric relaxation behavior. The increase in dielectric constant is considered to be due to the formation of microcrystals of SrTiO₃ and TiO₂ in the glass matrix. These glasses are n-type semiconductors as observed from the measurements of the thermoelectric power. Unlike many vanadate glasses, Long's overlapping large polaron tunnelling (OLPT) model is found to be most appropriate for fitting the experimental conductivity data, while for the undoped V₂O₅–Bi₂O₃ glasses, correlated barrier hopping conduction mechanism is valid. This is due to the change of glass network structure caused by doping base glass with SrTiO₃. The power law behavior (σ_ac=A(ω^s) with s<1) is, however, followed by both the doped and undoped glassy systems. The model parameters calculated are reasonable and consistent with the change of concentrations (x).     

Comparison of the developed thermal stresses in Al2O3–SG, ZrO2–12%Si+Al and ZrO2–SG coating systems subjected to thermal loading

In this investigation, thermal and structure finite element analysis has been employed to analyse the thermal stresses developed in Al₂O₃–SG, ZrO₂–12%Si+A1 and ZrO₂–SG.coatings subjected to thermal loading. Systems with 0.4 mm coating thickness and 4 mm substrate material thickness were modelled. Zirconia–spherical cast iron (SG) coatings with NiAl, NiCrAlY and NiCoCrAlY interlayers were also modelled. Nominal and shear stresses at the critical interface regions (film/interlayer/substrate) were obtained. The results showed that the lowest stress levels are in ZrO₂–SG coatings. Furthermore, the interlayer thickness and material combinations have a significant influence on the level of the developed thermal stresses. It is also concluded that the finite element technique can be used to optimise the design and the processing of ceramic coatings.     

Luminescence quenching by manganese ions in MO–CaF2–B2O3 glasses

Thermoluminescence (TL) characteristics of X-ray irradiated calcium fluoro borate glasses mixed with three different alkali oxide modifiers viz., Li₂O, Na₂O and K₂O have been studied in the temperature range 303–600 K; all the glasses have exhibited single TL peak at 485, 541 and 497 K respectively. The glasses containing Na₂O as modifier has exhibited the maximum TL light output. The doping of manganese oxide by a small concentration (0.2 mol%) in all these glasses has been observed to inhibit TL light output drastically with shifting of peak positions towards lower temperatures. The trap depth parameters associated with the observed TL peaks have been evaluated using Chen’s formulae. The probable mechanism responsible for quenching of TL emission by manganese ions in these glasses has been suggested with the aid of optical absorption, IR spectra and differential scanning calorimetric studies.     

Systematic search for energetically favored isomers of large fullerenes C122–C130 and C162–C180

Based on the methodology by Cioslowski et al. [J. Cioslowski, N. Rao, D. Moncrieff, J. Am. Chem. Soc. 122 (2000) 8265–8270], two empirical fit equations to predict the standard enthalpy of formation are obtained over large number of calculation results at B3LYP/6-31G* theory level for fullerene isomers, which can be used as a preliminary and second-level screening tool, respectively, for large fullerenes. By applying these equations in screening the whole isolated pentagon rule (IPR) isomers, the energetically favored isomers of large fullerenes C₁₂₂–C₁₃₀ and C₁₆₂–C₁₈₀ were predicted at the B3LYP/6-31G* density functional theory level for the first time. Our results show that the lowest energy isomers of C₁₇₄ (2473259: C_3v) and C₁₈₀ (4071832: I_h) possess much lower relative energy and larger HOMO–LUMO gaps. Moreover, the ionization energy and electron affinity of the lowest energy isomers were also investigated.