New phases in the systems EuF2:YF3 and EuF2:GdF3

Isothermal pseudo-binary phase studies of the systems EuF₂:YF₃ and EuF₂:GdF₃ have been completed at 1100°C. Three single phase regions corresponding to (1) EuF₃(ss); (a) hexagonal tysonite and (3) orthorhombic LnF₃(ss), Ln = Y, Gd, have been found. The single phase regions for both of these systems are similar and exist at 0–39, 73–82 and 91–100 mole % YF₃; 0–41, 70–77 and 85–100 mole % GdF₃.     

Ionic-liquid-assisted synthesis of YF3 with different crystalline phases and morphologies

YF₃ with different crystalline phases and morphologies have been prepared via a facile hydrothermal route assisted by imidazolium ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate (C₄mimBF₄) or 1-butyl-3-methylimidazolium hexafluorophosphate (C₄mimPF₆). The microstructures and morphologies of YF₃ particles were characterized by X-ray powder diffraction, X-ray photoelectron spectra (XPS), transmission electron microscopy (TEM), high resolution electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). Cubic and orthorhombic YF₃ were selectively synthesized by adjusting the molar ratio of the reagents and using C₄mimBF₄ as the fluoride source, while only orthorhombic YF₃ was obtained using C₄mimPF₆, indicating that the crystalline phases and morphologies of the products were significantly influenced by fluoride source and reaction media.     

Preparation, structure and dielectric properties of Ba4LaMNb3O15 (M = Ti, Sn ) ceramics

Two new cation-deficient hexagonal perovskites Ba₄LaMNb₃O₁₅ (M = Ti, Sn) ceramics were prepared by high temperature solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction, scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The Ba₄LaTiNb₃O₁₅ has high dielectric constant of 52, high quality factors (Q) 3500 (at 4.472 GHz), and temperature variation of resonant frequency (τ_f) +93 ppm °C⁻¹ at room temperature; Ba₄LaSnNb₃O₁₅ has dielectric constant of 39 with high Q value of 2510 (at 5.924 GHz), and τ_f −29 ppm °C⁻¹.     

Photoluminescence investigation of rare-earth activated GdCa3(GaO)3(BO3)4 phosphors under UV excitation

A borate compound was adopted as a new host material of Eu³⁺ and Tb³⁺ activators to fabricate efficient luminescence materials. The phosphor compositions, Gd_1−xEu_xCa₃(GaO)₃(BO₃)₄ and Gd_1−xTb_xCa₃(GaO)₃(BO₃)₄, were synthesized by conventional solid-state reactions. The crystalline phases of the resulting powders were identified using an X-ray diffraction system. Their photoluminescence properties were investigated under long-wavelength UV excitation. The Eu³⁺-doped and Tb³⁺-doped GdCa₃(GaO)₃(BO₃)₄ phosphors efficiently emitted red and green light, respectively. The temperature dependency of emission intensity was measured in a range from room temperature to 150 °C. The emission intensities of the red and green phosphors at 150 °C are 87% and 91% of those at room temperature, respectively. In addition, the decay times of both the red and green phosphors are shorter than 3 ms.     

New quenched-in fluorite-type materials in the Bi2O3-La2O3-PbO system: Synthesis and complex phase behaviour up to 750 °C

New quenched-in fluorite-type materials with composition (BiO_1.5)_0.94−x(LaO_1.5)_0.06(PbO)_x, x = 0.02, 0.03, 0.04 and 0.05, were synthesised by solid state reaction. The new materials undergo a number of phase transformations during heating between room temperature and 750 °C, as indicated by differential thermal analysis. Variable temperature X-ray diffraction performed on the material (BiO_1.5)_0.92(LaO_1.5)_0.06(PbO)_0.02 revealed that the quenched-in fcc fluorite-type material first undergoes a transformation to a β-Bi₂O₃-type tetragonal phase around 400 °C. In the range 450-700 °C, α-Bi₂O₃-type monoclinic, Bi₁₂PbO₁₉-type bcc and β₁/β₂-type rhombohedral phases, and what appeared to be a ?-type monoclinic phase, were observed, before a single-phase fluorite-type material was regained at 750 °C.     

Structural characterization of 0.5PbMg1/3Nb2/3O3-0.5BaxPb(1−x)TiO3 powders

The present work reports the effects caused by barium on phase formation, morphology and sintering of lead magnesium niobate-lead titanate (PMN-50PT). Ab initio study of 0.5Pb(Mg_1/3Nb_2/3)O₃-0.5(Ba_xPb_(1−x)TiO₃) ceramic powders, with x = 0, 0.20, and 0.40 was proposed, considering that the partial substitution of lead by barium can reestablish the equilibrium of monoclinic-tetragonal phases in the system. It was verified that even for 40 mol% of barium, it was possible to obtain pyrochlore-free PMN-PT powders. The increase of the lattice parameters of PMN-PT doped-powders confirmed dopant incorporation into the perovskite phase. The presence of barium improved the reactivity of the powders, with an average particle size of 120 nm for 40 mol% of barium against 167 nm for the pure sample. Although high barium content (40 mol%) was deleterious for a dense ceramic, contents up to 20 mol% allowed 95% density when sintered at 1100 °C for 4 h.     

Dielectric, electrical and magnetoelectric characterization of (x)Ni0.8Zn0.2Fe2O4 + (1 − x)Pb0.93La0.07(Zr0.60Ti0.40)O3 composites

The structural, electrical, dielectric, magnetic and magnetoelectric properties of (x)Ni_0.8Zn_0.2Fe₂O₄ + (1 − x)Pb_0.93La_0.07(Zr_0.60Ti_0.40)O₃ (x = 0, 0.15, 0.30, 0.45 and 1) have been studied by means of various experimental techniques. Polycrystalline samples of this series have been prepared by the double sintering ceramic method. X-ray diffraction data analysis revealed purity of the composites. Microstructural analysis using scanning electron microscopy mode depicts the presence of two phases in contact with each other. Dielectric properties were studied at and well above room temperature. Temperature dependent variation of the dielectric constant show diffused phase transition which can be well described by fitting the Lorentz-type relation, . Observation of well-saturated ferroelectric hysteresis loop and magnetic hysteresis loop for composites indicates that ferroelectric and magnetic ordering exist simultaneously at room temperature. The static value of magneto electric voltage coefficient (α_E) has been studied as a function of magnetic field at room temperature for all the composites. The maximum value of α_E is 7.53 mV/(cm Oe) for 85% PLZT-15% NZFO composites.     

Controlled synthesis of different morphological YF3 crystalline particles at room temperature

YF₃ crystalline particles with different crystal structures and different morphologies have been synthesized via a simple solution route by varying the fluoride source (NH₄F, HF, NH₄F·HF) and molar ratio of Y³⁺/F⁻ at room temperature. They were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray photoelectron spectrum (XPS).     

Supercritical hydrothermal synthesis of Cu2O(SeO3): Structural characterization, thermal, spectroscopic and magnetic studies

Cu₂O(SeO₃) has been synthesized in supercritical hydrothermal conditions, using an externally heated steel reactor with coupled hydraulic pump for the application of high pressure. The compound crystallizes in the P2₁3 cubic space group. The unit cell parameter is a = 9.930(1) Å with Z = 12. The crystal structure has been refined by the Rietveld method. The limit of thermal stability is, approximately, 490 °C. Above this temperature the compound decomposes to SeO₂(g) and CuO(s). The IR spectrum shows the characteristic bands of the (SeO₃)²⁻ oxoanion. In the diffuse reflectance spectrum two intense absorptions characteristic of the Cu(II) cations in five-coordination are observed. The ESR spectra are isotropic from room temperature to 5 K, with g = 2.11(2). The thermal evolution of the intensity and line width of the signals suggest a ferromagnetic transition in the 50-45 K range. Magnetic measurements, at low temperatures, confirm the existence of a ferromagnetic transition with a critical temperature of 55 K.     

High temperature structural phase transitions in SrSnO3 perovskite

Three high temperature structural phase transitions have been identified in the perovskite-structured phase SrSnO₃ using differential scanning calorimetry and dilatometry, and have subsequently been structurally characterised using high-resolution neutron powder diffraction. Between 298 and 905 K, SrSnO₃ is orthorhombic, space group Pmcn before undergoing a continuous phase transition to a second orthorhombic phase in space group Incn. At 1062 K there is a first order phase transition to a tetragonal phase in space group I4/mcm before finally transforming to the aristotype phase at 1295 K. Using the magnitude of the anti-phase tilt as a measure of the order parameter for the transition from I4/mcm to suggests this transition is tricritical in nature. Crystal structures are reported for the three hettotype phases.     

High-pressure phase transition in Ho2O3

High-pressure X-ray diffraction and Raman studies on holmium sesquioxide (Ho₂O₃) have been carried out up to a pressure of ∼17 GPa in a diamond-anvil cell at room temperature. Holmium oxide, which has a cubic or bixbyite structure under ambient conditions, undergoes an irreversible structural phase transition at around 9.5 GPa. The high-pressure phase has been identified to be low symmetry monoclinic type. The two phases coexist to up to about 16 GPa, above which the parent phase disappears. The high-pressure laser-Raman studies have revealed that the prominent Raman band ∼370 cm⁻¹ disappears around the similar transition pressure. The bulk modulus of the parent phase is reported.     

Comparative investigation of structure and dielectric properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) and 10% PbZrO3-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) ceramics prepared by a modified precursor method

Relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) and 10% PbZrO₃-doped Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics were both prepared by a modified precursor method, which was based on the high-temperature synthesis of an oxide precursor that contained all the B-site cations for the consideration of B-site homogeneity. The dielectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramic was more of normal ferroelectric behavior, but the high dielectric constant (?_m = 34,200 at 1 kHz) and piezoelectric constant (d₃₃ = 709 pC/N) were observed for this composition close to the morphotropic phase boundary. Comparatively, introduction of 10% PbZrO₃ into Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics enhanced the diffuse phase transition as well as the rhombohedral to tetragonal phase transition temperature, while it also kept the high dielectric constant (?_m = 29,600 at 1 kHz) and piezoelectric constant (d₃₃ = 511 pC/N).     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

Synthesis and upconversion emission of rare earth-doped olive-like YF3 micro-particles

The olive-like YF₃ micro-particles were fabricated via a two-step route. The precursor NH₄Y₃F₁₀ nano-cages sized 8 nm with hollow interiors were first synthesized in a solid reaction at room temperature. In the course of subsequent hydrothermal treating, the unstable NH₄Y₃F₁₀ nano-cages were decomposed, resulted in the formation of Y(OH)_1.63F_1.37 micro-tubes. Prolonging the hydrothermal reaction induced the further decomposition of Y(OH)_1.63F_1.37 to produce YF₃ nano-crystals, which then aggregated together forming the final olive-like YF₃ micro-particles. For the Er³⁺/Yb³⁺ co-doped olive-like YF₃ micro-particles, intense visible upconversion emissions were measured under 976 nm excitation owing to the partition of rare earth ions in the lattice, indicating this material a promising luminescent host.     

Structure and ferroelectric properties in (K0.5Bi0.5)TiO3-BiScO3-PbTiO3 piezoelectric ceramic system

(K_0.5Bi_0.5)TiO₃-BiScO₃-PbTiO₃ ceramics were synthesized by conventional solid-state method. A morphotropic phase boundary (MPB) was confirmed with the aid of structural analysis. Two dielectric anomalous peaks were observed, the one around dielectric maximum temperature (T_m) due to phase transformation from ferroelectric to paraelectric while the second one could be ascribed to space charges. Furthermore, the existence of space charges also resulted in the independence of T_m with frequency at low lead composition. A new high temperature piezoelectric ceramic, 0.30(K_0.5Bi_0.5)TiO₃-0.30BiScO₃-0.40PbTiO₃ close to MPB exhibited excellent electrical properties with T_m of 384 °C, d₃₃ of 247 pC/N, k_p of 38.9%, P_r of 19.41 μC/cm², and E_c of 2.25 kV/mm, indicative of a candidate for high temperature application.     

Structural and transport properties of SrRuO3 thin films grown by MOCVD on (0 0 1) SrTiO3 substrates: The role of built-in strain and extra phases

Pure SrRuO₃ (SRO) thin films and SRO thin films containing the extra metallic phases Ru, RuO₂ and Sr₃Ru₂O₇ were deposited by MOCVD on (0 0 1) SrTiO₃ substrates under different conditions (Ru/Sr and Ar/O₂ ratio in the gas phase, substrate temperature, supersaturation). The single-phase compressively-strained SRO film is of high structural quality and shows a ferromagnetic transition at a suppressed Curie temperature (T_c) of about 142 K and low electrical resistivity (230 μΩ cm). Under certain deposition conditions Ru and RuO₂ extra phases form leading to a reduced room temperature resistivity of 100 μΩ cm. On the other hand, the presence of Sr₃Ru₂O₇ increases the resistivity to 385 μΩ cm. We have observed that the existence of the extra phases caused a slight shift of T_c towards the bulk value, while relaxation of the lattice strain resulted in increase of T_c to 160 K. The deviation from the stoichiometric composition in films with extra phases is also confirmed by the residual electrical resistivity ratio. On the other hand, the pure SRO films, the compressively strained and the plastically relaxed exhibit a stoichiometric ratio.     

Crystal growth and characterization of Yb-doped Gd3Ga5O12

Single crystals of (Yb_xGd_1−x)₃Ga₅O₁₂ (0.0 ≤ x ≤ 1.0) have been grown by the micro-pulling-down method. Formation of continuous solid solutions with a garnet structure was confirmed. Composition dependence of the lattice constant, thermal diffusivity, specific heat capacity and thermal conductivity was investigated. Assignment of the Yb³⁺-energy levels in Gd₃Ga₅O₁₂-host lattice has been performed by using absorption, emission and Raman spectroscopy measurements at both, room temperature and at 12 K.     

Impact of ethylene carbonate on ion transport characteristics of PVdF-AgCF3SO3 polymer electrolyte system

The ionic transport in thin film plasticized polymer electrolytes based on polyvinylidene fluoride (PVdF) as the polymer host, silver triflate (AgCF₃SO₃) as salt and ethylene carbonate (EC) as plasticizer prepared by solution casting technique has been reported. Addition of silver triflate has resulted in an increase in the room temperature (298 K) electrical conductivity of the polymer from 10⁻⁶ to 10⁻⁵ S cm⁻¹ whereas incorporation of EC as the plasticizer has further enhanced the conductivity value by an order of magnitude to 10⁻⁴ S cm⁻¹ owing to the possible decrease in crystallinity of the polymer matrix as revealed by the detailed temperature-dependent complex impedance, silver ionic transference number, Fourier transform infrared and X-ray diffraction measurements.     

Enhancement of thermoelectric figure of merit by doping Dy in La0.1Sr0.9TiO3 ceramic

Ceramic samples of La_0.1Sr_0.9−xDy_xTiO₃ (x = 0.01, 0.03, 0.07, 0.10) have been prepared by the solid-state reaction method. Characterization from the powder X-ray diffraction indicates that their crystal structure changes from cubic to tetragonal phase. Their electrical and thermal transport properties are measured in the temperature range of 300-1100 K. n-Type thermoelectric is obtained with large Seebeck coefficient. The figure of merit is markedly improved, due to relatively lower electrical resistivity and thermal conductivity by Dy doping effect. A much lower electrical resistivity of 0.8 mΩ cm at room temperature is obtained in La_0.1Sr_0.8Dy_0.1TiO₃, and with a relatively lower thermal conductivity of 2.5 W/m K at 1075 K. The maximum figure of merit reaches ∼0.36 at 1045 K for La_0.1Sr_0.83Dy_0.07TiO₃, which is the largest value among n-type oxide thermoelectric ceramics.     

Effect of BaTiO3 additive on the electrical properties of Na0.50Bi0.50TiO3 lead free ceramics

The near morphotropic phase boundary (MPB) compositions of lead-free piezoelectric ceramics based on sodium bismuth titanate (Na_0.50Bi_0.50TiO₃: NBT) and barium titanate (BaTiO₃: BT) were carefully investigated by conventional high temperature mixed-oxide method. All the ceramics exhibit single phase rhombohedral symmetry. The frequency (100 Hz to 1 MHz) and temperature (Room temperature–500 °C) dependence of impedance spectroscopy of (1 − x)Na_0.50Bi_0.50TiO3–xBaTiO₃ (x = 0.0, 0.06, 0.07 and 0.08) ceramics were investigated by impedance analyzer. The frequency explicit plots of Z″ versus frequency at various temperatures show peaks in the higher temperature range (>400 °C). The compounds show dielectric relaxation, which is found to be of non-Debye type and the relaxation frequency shifted to higher side with increase in temperature. The activation energy values obtained for different BT content suggest that the electrical conduction in NBT is mainly due to the mobility of the ionized oxygen defects.