Nanocrystallization of SrBi2Nb2O9 from glasses in the system Li2B4O7---SrO---Bi2O3---Nb2O5

Transparent glasses in the system (100−x)Li₂B₄O₇–x(SrO---Bi₂O₃---Nb₂O₅) (10≤x≤60) (in molar ratio) were fabricated by a conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via X-ray powder diffraction (XRD) and differential thermal analyses (DTA) respectively. Glass–ceramics embedded with strontium bismuth niobate, SrBi₂Nb₂O₉ (SBN) nanocrystals were produced by heat-treating the as-quenched glasses at temperatures higher than 500 °C. Perovskite SBN phase formation through an intermediate fluorite phase in the glass matrix was confirmed by XRD and transmission electron microscopy (TEM). Infrared and Raman spectroscopic studies corroborate the observation of fluorite phase formation. The dielectric constant (_r) and the loss factor (D) for the lithium borate, Li₂B₄O₇ (LBO) glass comprising randomly oriented SBN nanocrystals were determined and compared with those predicted based on the various dielectric mixture rule formalism. The dielectric constant was found to increase with increasing SBN content in LBO glass matrix.     

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.     

Optical bistability for ZnO–Nb2O5–TeO2 glasses

We examined the optical nonlinear properties of ZnO–Nb₂O₅–TeO₂. The absorption and Raman spectra were measured, the third-order nonlinear susceptibility was determined by degenerated four wave mixing technique. The magnitude of χ⁽³⁾ is about 1.0 × 10⁻¹² esu, larger than that of silica glasses, and the optical bistability was observed in a Fabry–Perot cavity.     

Phase relations, lattice thermal expansion in Ce1−xEuxO2−x/2 and Ce1−xSmxO2−x/2 systems and stabilization of cubic RE2O3 (RE: Eu, Sm)

The phase relations in CeO₂–Eu₂O₃ and CeO₂–Sm₂O₃ systems have been established under slow-cooled conditions from 1400 °C. The two-phase relations differ as the CeO₂–Eu₂O₃ system showed only two monophasic phase fields, namely F-type cubic and C-type cubic, whereas CeO₂–Sm₂O₃ system showed three phase fields namely F-type cubic, C-type cubic and a biphasic field comprising of C-type cubic and monoclinic phase. An interesting observation of this investigation is the stabilization of C-type rare-earth oxide after Ce⁴⁺ substitution, which is attributed to decrease in average cationic size on Ce⁴⁺ substitution at RE³⁺ site. The lattice thermal expansion behavior of F-type solid solution and C-type solid solution in CeO₂–Eu₂O₃ system was investigated by high-temperature XRD.     

Synthesis and structural characterization of mesoporous V2O5 thin films for electrochromic applications

Mesoporous vanadium pentoxide (V₂O₅) films have been synthesized by hydrolysis of vanadium tri-isopropoxide (VO(OC₃H₇)₃) in the presence of polyethylene glycol (PEG) as a structure-directing agent. The structure, the stoichiometry and the morphology of the films have been studied as a function of the thermal annealing by X-ray diffraction (XRD), micro-Raman spectroscopy, optical microscopy, scanning electron microscopy and atomic force microscopy. XRD patterns and Raman spectra show the presence of two previously unreported crystalline phases. The PEG:V₂O₅ molar ratio affects the temperature of phase formation, the amount and even the order in which the phases appear. The morphological characterization underlines the role of the surfactant to promote porous networks, formed by micrometric clusters of controlled shapes and patterns embedded in a homogeneous host matrix.     

Synthesis and Li ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass-ceramics

Glasses with the compositions of xLi₂O-(70 − x)Nb₂O₅-30P₂O₅, x = 30-60, and their glass-ceramics are synthesized using a conventional melt-quenching method and heat treatments in an electric furnace, and Li⁺ ion conductivities of glasses and glass-ceramics are examined to clarify whether the glasses and glass-ceramics prepared have a potential as Li⁺ conductive electrolytes or not. The electrical conductivity (σ) of the glasses increases monotonously with increasing Li₂O content, and the glass of 60Li₂O-10Nb₂O₅-30P₂O₅ shows the value of σ = 2.35 × 10⁻⁶ S/cm at room temperature and the activation energy (E_a) of 0.48 eV for Li⁺ ion mobility in the temperature range of 25-200 °C. It is found that two kinds of the crystalline phases of Li₃PO₄ and NbPO₅ are formed in the crystallization of the glasses and the crystallization results in the decrease in Li⁺ ion conductivity in all samples, indicating that any high Li⁺ ion conducting crystalline phases have not been formed in the present glasses. 60Li₂O-10Nb₂O₅-30P₂O₅ glass shows a bulk nanocrystallization (Li₃PO₄ nanocrystals with a diameter of ∼70 nm) and the glass-ceramic obtained by a heat treatment at 544 °C for 3 h in air exhibits the values of σ = 1.23 × 10⁻⁷ S/cm at room temperature and E_a = 0.49 eV.     

Structural and optical properties of pulsed laser deposited V2O5 thin films

Pulsed laser deposited nanocrystalline V₂O₅ thin films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM) and optical spectroscopy. The films were deposited on amorphous glass substrates, keeping the O₂ partial pressure at 13.33 Pa and the substrate temperature at 220 °C. The characteristics of the films were changed by varying the laser fluence and repetition rate. XRD revealed that films are nanocrystalline with an orthorhombic structure. XPS shows the sub-stoichiometry of the films, that generally relies on the fact that during the formation process of V₂O₅ films, lower valence oxides are also created. From the HRTEM images, we observed the size evolution and distribution characteristics of the clusters in the function of the laser fluence. From the spectral transmittance we determined the absorption edge using the Tauc plot. Calculation of the Bohr radius for V₂O₅ is also reported.     

Structural and dielectric properties of ferroelectric Sr1−xBaxBi2(Nb0.5Ta0.5)2O9 and Sr0.5Ba0.5Bi2(Nb1−yTay)2O9 ceramics

Ferroelectric Sr_1−xBa_xBi₂(Nb_0.5Ta_0.5)₂O₉ and Sr_0.5Ba_0.5Bi₂(Nb_1−yTa_y)₂O₉ were synthesized by solid state reaction route. X-ray diffraction studies confirm the formation of single phase layered perovskite solid solutions over a wide range of compositions (x=y=0.0, 0.25, 0.50, 0.75 and 1). The lattice parameters and the Curie temperature (T_c) have been found to have linear dependence on x and y. Transmission electron microscopy (TEM) suggest the lowering of orthorhombic distortion with increasing Ba²⁺ substitution. Variations in microstructural features as a function of x and y were monitored by scanning electron microscopy (SEM). The dielectric constant at room temperature increases with increase in both x and y. Interestingly Ba²⁺ substitution on Sr²⁺ site induces diffused phase transition and diffuseness increases with increasing Ba²⁺ concentration.     

Temperature-dependent oxygen release, intercalation behaviour and catalytic properties of V2O5·xNb2O5 compounds

In order to investigate the catalytic properties, V_2,38Nb_10,7O_32,7, VNb₉O₂₅ and solid solutions of V₂O₅ in TT-Nb₂O₅ were prepared by thermal decomposition of freeze-dried oxalate precursors. The samples were characterised by X-ray diffraction and surface area determination. The crystalline samples are capable of the intercalation of sodium and lithium ions from solution. Above a temperature of about 500 °C, in dependence on the oxygen partial pressure a reversible release and uptake of oxygen without a structural variation takes place. The catalytic properties have been evaluated for the oxidative dehydrogenation (ODH) of propane and propene. There are only small differences in the catalytic activity of the different crystalline samples. Because of the relative high starting temperature, a selective catalytic oxidation of propane to propene is hardly observed.     

Microstructure, hysteresis and microwave absorption analysis of Ba(1 − x)SrxFe12O19 ferrite

M-type hexagonal ferrite series, Ba_(1−x)Sr_xFe₁₂O₁₉ (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0), has been synthesized by conventional ceramic method. Hysteresis parameters have been investigated at an applied field of 10 kOe and absorption has been studied at X-band as a function of thickness, substitution and frequency. Microstructure and X-ray diffraction confirmed hexagonal structure of ferrite. The substitution causes profound increase in absorption, coercivity and magnetization. The magnetic parameters have been characterized by taking into account microstructure and preferential site occupancy. Curie temperature decreases with substitution due to the formation of spin canting structure.     

Morphological, structural, optical and dielectric properties of 91SiO2:4Li2O:4Nb2O5:1Dy2O3 (% mole) glass prepared by sol–gel

We report on the structural, morphological and optical characterization of glass and glass–ceramic samples, with nominal composition of 91SiO₂:4Li₂O:4Nb₂O₅:1Dy₂O₃ (% mole). The samples were heated treated in air in the temperature range between 500 °C and 800 °C. The glass–ceramics samples start to crystallize at temperatures above 600 °C and besides the SiO₂ and LiNbO₃ crystalline phases, sub micron DyNbO₄ precipitates were identified by X-ray diffraction and scanning electron microscopy for temperatures above 750 °C. Using Raman spectroscopy was possible to identify the vibration modes assigned to the crystalline phases detected by the XRD analysis. Also, the performed Photoluminescence Spectroscopy analysis suggest that the optical activation of Dy³⁺ ions in the glass and glass–ceramics hosts was found to be dependent of the heat treatment temperature. Intraconfigurational transitions between the ⁴F_9/2 and ⁶H_{J(=15/2, 13/2)} multiplets of Dy³⁺ ions were only observed for samples without the presence of the DyNbO₄ crystalline phase. Moreover, for samples heat treated between 500 °C and 700 °C the intensity ratio of the ⁴F_9/2⁶H_13/2 and ⁴F_9/2⁶H_15/2 transitions of the lanthanide ion changes, suggesting different ion environments which are dependent on the thermal annealing temperature. The dielectric measurements revealed that ε′ value depends mainly in the number of network modifier ions and the relaxation phenomenon observed at frequencies above 10 kHz, in all samples, can be assigned to the increase of the volume ratio between the LiNbO₃ particles and the glass network.     

Dependence of optical properties on the composition in Er-doped xNaPO3–(80 − x)TeO2–10ZnO–10Na2O glasses

Transparent and uniform tellurite–phosphate glasses were prepared and the reason why the substitution of NaPO₃ for P₂O₅ can eliminate the coloration of tellurite–phosphate was discussed. The result of TDA indicated that introducing NaPO₃ into tellurite glasses can improve thermal stability of glass hosts. The compositional dependence of absorption cross-sections of ⁴I_13/2, ⁴I_11/2 and ²H_11/2 level, emission cross-section of ⁴I_13/2 level, host phonon energy, up-conversion and 1.5 μm optical emission intensity as well as and quantum yield for ⁴I_13/2 level in PTEr glasses were investigated too. By analyzing obtained data, authors believe that tellurite–phosphate glasses can be used as potential host material for developing optical amplifiers.     

Spectral analysis of RE (RE = Sm, Dy, and Tm): P2O5–Al2O3–Na2O glasses

Phosphate glasses in the compositions of 70P₂O₅–15Al₂O₃–14Na₂O–1RE³⁺ (RE = Sm, Dy, and Tm) (mol%) were prepared by melt-quenching technique and characterized optically. The differential thermal analysis (DTA) profile of the host glass was carried out to confirm its thermal stability. For all the glasses absorption, photoluminescence and decay measurements have also been carried out. These glasses have shown strong emission and absorption bands in visible and near-infrared (NIR) region. From the measured absorption spectra, Judd–Ofelt (J–O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. For Sm³⁺ doped glass, four emission bands centered at 562 nm (⁴G_5/2 → ⁶H_5/2), 598 nm (⁴G_5/2 → ⁶H_7/2), 644 nm (⁴G_5/2 → ⁶H_9/2), and 704 nm (⁴G_5/2 → ⁶H_11/2) have been observed with 402 nm (⁶H_5/2 → ⁴F_7/2) excitation wavelength. Of them, 598 nm (⁴G_5/2 → ⁶H_7/2) has shown a bright orange emission. With regard to Dy³⁺ doped glass, a blue emission band centered at 486 nm (⁴F_9/2 → ⁶H_15/2) and a bright yellow emission at 575 nm (⁴F_9/2 → ⁶H_13/2) have been observed, apart from 662 nm (⁴F_9/2 → ⁶H_11/2) emission transition with an excitation at 388 nm (⁶H_15/2 → ⁴I_13/2,⁴F_7/2) wavelength. Emission bands of 650 nm (¹G₄ → ³F₄) and 785 nm (¹G₄ → ³H₅) transitions for the Tm³⁺ doped glass, with an excitation wavelength at 466 nm (³H₆ → ¹G₄), have also been observed. The stimulated emission cross-sections of all the emission bands of RE³⁺ glasses (RE = Sm, Dy, and Tm) have been computed based on their measured full-width at half maximum (FWHM, Δλ) and measured lifetimes (τ_m).     

Synthesis of layered Li1.2+x[Ni0.25Mn0.75]0.8−xO2 materials (0 ≤ x ≤ 4/55) via a new simple microwave heating method and their electrochemical properties

Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) was prepared by a new simple microwave heating method and the effect of extra Li⁺ content on electrochemistry of Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) was firstly revealed. X-ray diffraction identified that they had layered α-NaFeO₂ structure (space group R-3m). Linear variation of lattice constant as a function of x value supported the formation of solid solution, that is, extra Li⁺ is possibly incorporated in structure of layered Li_1.2Ni_0.2Mn_0.6O₂ (x = 0), accompanying oxidization of Ni²⁺ to Ni³⁺ to form Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55). This was confirmed by X-ray photoelectron spectroscopy that Ni³⁺ appeared and increased in content with increasing x value. Charge–discharge tests showed that Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) truly displayed different electrochemical properties (different initial charge–discharge plots, capacities and cycleability). Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) in this work delivered the highest discharge capacity of 219 mAh g⁻¹ between 4.8 and 2.0 V. Increasing Li content (x value in Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂) reduced charge–discharge capacities, but significantly enhancing cycleability.     

Study of dielectric, magnetic and ferroelectric properties in Bi1 − xGdxFeO3

Gd-doped BiFeO₃ polycrystalline ceramics were synthesized by solid-state reaction method and their dielectric and magnetic properties were investigated. X-ray diffraction pattern showed that Bi_1 − xGd_xFeO₃ (x = 0, 0.05 and 0.1) ceramics were rhombohedral. The Gd substitution has suppressed the usual impurity peaks present in the parent compound and we obtained single phase Bi_0.9Gd_0.1FeO₃ ceramic. Gd substitution reduced the antiferromagnetic Néel temperature (T_N) in Bi_1 − xGd_x FeO_3. An anomaly in the dielectric constant(ε) and dielectric loss(tan (δ)) in the vicinity of the antiferromagnetic Néel temperature (T_N) was observed. Ferroelectric and magnetic hysteresis loops measured at room temperature indicated the coexistence of ferroelectricity and magnetism. The room temperature magnetic hysteresis loops were not saturated, but the magnetic moment was found to increase with increase in Gd concentration.     

A low-temperature reactive sintering process for the 5Li2O–1Nb2O5–5TiO2 microwave dielectric ceramics

The B₂O₃-doped 5Li₂O–1Nb₂O₅–5TiO₂ composite microwave dielectric ceramics prepared by conventional and low-temperature single-step reactive sintering processes were investigated in the study. Without any calcinations involved, the Nb₂O₅ mixture of Li₂CO₃ and TiO₂ was pressed and sintered directly in the reactive sintering process. More uniform and finer grains could be obtained in the 5Li₂O–1Nb₂O₅–5TiO₂ ceramics by reactive sintering process, which could effectively save energy and manufacturing cost. And relatively good microwave dielectric properties of _r = 41, Q × f = 9885 GHz and τ_f = 43.6 ppm/°C could be obtained for the 1 wt.% B₂O₃-doped ceramics reactively sintered at 900 °C.     

Thermal nonlinear refraction in the dye-doped sol–gel xTiO2 · (100 − x)SiO2 system

The build-up time of the thermal lens effect induced by a Gaussian beam in the DO3-doped sol–gel system xTiO₂ · (100 − x)SiO₂ at different compositions, both in the liquid and gel phases has been measured in a Z-scan geometry. While the pure titania samples show a minimum of the thermal diffusivity, a maximum is found for x ≈ 30. The sol to gel transformation leads to an increase of the build-up times at all compositions.     

Thermal expansion properties of Ln2−xCrxMo3O12 (Ln = Er and Y)

Structures and thermal expansion properties of Ln_2−xCr_xMo₃O₁₂ (Ln = Er and Y) have been investigated by X-ray powder diffraction. Rietveld analysis results of Ln_2−xCr_xMo₃O₁₂ indicate that compounds Er_2−xCr_xMo₃O₁₂ (0 ≤ x ≤ 0.3) and Y_2−xCr_xMo₃O₁₂ (0 ≤ x ≤ 0.2) crystallize in orthorhombic structure and exhibit negative thermal expansion, while both monoclinic and orthorhombic compounds Er_2−xCr_xMo₃O₁₂ (1.7 ≤ x ≤ 2.0) and Y_2−xCr_xMo₃O₁₂ (1.8 ≤ x ≤ 2.0) possess positive coefficient of thermal expansion. The coefficients of linear thermal expansion of orthorhombic Ln_2−xCr_xMo₃O₁₂ change from negative to positive with increasing chromium content. Thermogravimetric and differential scanning calorimetry have been used to study the hygroscopicity and the phase transition temperature.     

Synthesis and characterization of LiCo0.3−xGaxNi0.7O2 (x = 0, 0.05) as a cathode material for lithium ion battery

The single phase of LiCo_0.3−xGa_xNi_0.7O₂ (x = 0, 0.05) was synthesized by a sol–gel method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical performance. The powders are homogeneous and have a good-layered structure. The synthesized LiCo_0.25Ga_0.05Ni_0.7O₂ exhibits better electrochemical performance with an initial discharge capacity of 180.0 mAh g⁻¹ and a capacity retention of 95.2% after 50 cycles between 2.8 and 4.4 V at 0.2C rate. The study on the structural evolution of the material during the cycling shows that Ga-doping improves the structure stability of LiCo_0.3Ni_0.7O₂ at ambient temperature and 55 °C. Meanwhile, Ga-doping not only suppresses the alternating current (AC) impedance of LiCo_0.3Ni_0.7O₂ but also promotes the Li⁺ diffusion in LiCo_0.3Ni_0.7O₂. Furthermore, thermal stability of the charged LiCo_0.25Ga_0.05Ni_0.7O₂ is improved, which may be attributed to the retard of O₂ evolution in LiCo_0.3Ni_0.7O₂ and the suppression of electrolyte oxidation during cycling by Ga-doping_.     

Polar nanodomains and relaxor behaviour in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 crystals with x = 0.3–0.5

Phase transitions and dielectric properties of the (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ crystals with x = 0.3–0.5 are studied. The solid solutions in this composition range are shown to be relaxor ferroelectrics. The crystals with low x demonstrate a diffused maximum in the temperature dependences of the dielectric permittivity at T_m. T_m varies with frequency according to the Vogel–Fulcher law. The polarizing microscopy investigations reveal a first-order phase transition from the relaxor phase to the low-temperature ferroelectric phase at T_C, which is several degrees below T_m. The permittivity peak in the crystals with x = 0.5 is sharp, and T_m is equal to T_C and does not depend on frequency, as is typical of the transition from a ferroelectric to an ordinary paraelectric phase. Nevertheless, the relaxor, but not the paraelectric, phase is observed at T > T_m. This conclusion is confirmed by the observation of the temperature behaviour of complex dielectric permittivity at T > T_m, which is typical of relaxors and related to the existence of polar nanodomains.