One-dimensional Bi<Subscript>2</Subscript>Mo<Subscript>x</Subscript>W<Subscript>1-x</Subscript>O<Subscript>6</Subscript> sosoloids: controllable synthesis by electrospinning process and enhanced photocatalytic performance

One-dimensional Bi₂Mo_xW_1-xO₆ (x = 0, 0.2, 0.5, 0.67, and 1) photocatalysts have been successfully synthesized for the first time by a straightforward electrospinning technique with a calcination process. The as-formed Bi₂Mo_xW_1-xO₆ nanofibers are composed of inter-linked nanosheets of 30–50 nm in size and characterized by thermogravimetric and differential scanning calorimetric, Fourier transform infrared, Raman spectra, X-ray powder diffraction, scanning electron microscope, Brunauer-Emmett-Teller, transmission electron microscope, UV-Vis spectroscopy, photoluminescence, HPLC, and EIS. The photodegradation behaviors towards organic dyes, including rhodamine B (RhB) and methylene blue (MB) are investigated, and the results illustrate that Bi₂Mo_0.25W_0.75O₆ nanofibers exhibit the highest photocatalytic performance under visible light irradiation than Bi₂Mo_xW_1-xO₆ (x = 0, 0.2, 0.5, 0.67, and 1) samples. The possible mechanisms of the enhanced photocatalytic properties are discussed in detail.     

Solid state synthesis of nonstoichiometric Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> composites as visible-light photocatalyst

Nonstoichiometric Bi₂WO₆ photocatalyst with the composition of Bi_2?+?x WO_6?+?1.5x (?0.25 ≤ x ≤ 1) wa synthesized by a facile solid state reaction method. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-vis absorption spectrum. The Bi_2.5WO_6.75 photocatalyst showed excellent visible-light-driven photocatalytic performance; nearly 100 % of RhB (10 ppm, pH?=?3?~?4) was decomposed within 25 min, which demonstrated that nonstoichiometric semiconductors could be an efficient visible-light-driven photocatalyst.     

Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanosquaresheets grown on Si substrate

A novel morphology of Bi₂O₃ nanomaterial (nanosquaresheets) has been successfully synthesized in large area by thermal evaporation of commercial Bi₂O₃ powder at high temperatures. The Bi₂O₃ nanosquaresheets (NSSs) are perfect regular squares and have sharp, uniform edges. The typical length of the sides is in the range of 200–600 nm. The thickness varies from 30 to 100 nm. Electron microscopy observations show that the Bi₂O₃ NSSs are single crystalline. The growth of Bi₂O₃ NSSs is probably controlled by a vapor–solid mechanism. The dominate growth directions are [2̄10] and [1̄2̄2] within the (245) planes. PACS 81.05.Hd; 81.10.Bk; 81.16.Be     

Controlled synthesis of photoluminescent Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> nanoparticles from metal-organic polymeric precursor

Bi₄Ti₃O₁₂ (BIT) nanoparticles with a narrow average particle size distribution in the range of 11–46 nm was synthesized via a metal-organic polymeric precursor process. The crystallite size and lattice parameter of BIT were determined by XRD analysis. At annealing temperatures >550 °C, the orthorhombic BIT compound with lattice parameters a = 5.4489 Å, b = 5.4147 Å, and c = 32.8362 Å was formed while at lower annealing temperatures orthorhombicity was absent. Reaction proceeded via the formation of an intermediate phase at 500 °C with a stoichiometry close to Bi₂Ti₂O₇. The particle size and the agglomerates of the primary particles have been confirmed by FESEM and TEM. The decomposition of the polymeric gel was ascertained in order to evaluate the crystallization process from TG-DSC analysis. Raman spectroscopy was used to investigate the lattice dynamics in BIT nanoparticles. In addition, investigation of the dependence of the visible emission band around the blue–green color emission on annealing temperatures and grain sizes showed that the effect of grain size plays important roles, and that oxygen vacancies may act as the radiative centers responsible for the observed visible emission band.     

Hydrothermal synthesis and electrochemical performance of Mn-doped V<Subscript>6</Subscript>O<Subscript>13</Subscript> as cathode material for lithium-ion battery

Mn_xV_6?xO₁₃ (x?=?0.01, 0.02, 0.03, 0.04) were successfully synthesized via a simple hydrothermal method followed by heat-treatment. Both crystal domain size, electronic conductivity and the lithium diffusion coefficient of the Mn_xV_6?xO₁₃ samples were influenced by the doping amount of Mn²⁺. When x?=?0.02, the product was nano-sized particles and exhibited the best electrochemical performance. The enhanced electrochemical performance originated from its higher total conductivity and higher lithium diffusion coefficient.     

Spectral-luminescent investigations of glasses and glass-ceramic materials in Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Glasses of 2Bi₂O₃-3GeO₂-xFe₂O₃ composition, where x = 0–1.5, are obtained under oxidizing and reducing conditions. Glass-ceramic materials are produced by the thermal treatment of the glasses, the properties of which, as well as those of the original glasses, are studied by the methods of X-ray phase analysis and optical and luminescent spectroscopy. It is found that the Fe³⁺/Fe²⁺ ion ratio in the samples changes depending on the synthesis conditions of the original glasses and crystallization process.     

Phase transition in Bi<Subscript>8</Subscript>Fe<Subscript>6</Subscript>Ti<Subscript>3</Subscript>O<Subscript>27</Subscript> multiferroic ceramics

The polycrystalline Bi₈Fe₆Ti₃O₂₇ compound was prepared by a high-temperature solid-state reaction technique. Preliminary structural analysis by X-ray diffraction (XRD) confirms the formation of a single-phase compound in an orthorhombic crystal system at room temperature. The elemental content of the compound was analyzed by EDAX microanalysis. Microstructural analysis by scanning electron microscopy (SEM) shows that the compound has well defined grains, which are distributed uniformly throughout the surface of the pellet sample. Detailed studies of temperature-dependent dielectric response at various frequencies show dielectric anomalies at 380, 389 and 403°C for 10 kHz, 100 kHz, and 1 MHz respectively. The hysteresis loop observed by applying an electric field of 12 kV/cm on the poled sample with smaller remanent polarization supports the existence of ferroelectricity in this material. The value of d₃₃ of the compound was found to be 19 pC/N.      

Thermal physical properties of Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> single crystals

The heat capacity, thermal conductivity, thermal diffusivity, and thermal expansion of Bi₄Ge₃O₁₂ single crystals have been measured over a wide temperature range.     

Electrical properties of Sr<Subscript>3</Subscript>Bi<Subscript>4</Subscript>Ti<Subscript>6</Subscript>O<Subscript>21</Subscript> thin films

Highly c-axis-oriented Sr₃Bi₄Ti₆O₂₁ (SBTi) thin films were fabricated on Pt-coated Si substrates by pulsed laser deposition (PLD). The structures were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). No peaks of SrTiO₃ (STO) could be detected in the XRD pattern, indicating the existence of the SBTi single phase. Good ferroelectric hysteresis loops of the films with Pt electrodes were obtained. With an applied field of 400 kV/cm, the measured remanent polarization (P_r) and coercive field (E_c) values were 4.1 C/cm² and 75 kV/cm respectively. The films showed little fatigue after 2.22×10⁹ switching cycles: the nonvolatile polarizations decreased by less than 5% of the initial values. The dielectric constant and the loss tangent of the films were measured to be 363 and 0.04 at 100 kHz. These results might be advantageous for nonvolatile ferroelectric random access memory (NVFRAM) and dynamic random access memory (DRAM). PACS 77.84.Dy; 77.22.-d; 68.55.Jk     

Impedance analysis of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric ceramic

AC impedance spectroscopy technique has been used to study electrical properties of Bi_3.25La_0.75Ti₃O₁₂ (BLT) ceramic. Complex impedance plots were fitted with three depressed semicircles, which are attributed to crystalline layer, plate boundary and grain boundary and all three were found to comprise of universal capacitance nature [C = C0w ⁿ⁻¹]. Grain boundary resistance and capacitance evaluated from complex impedance plots have larger values than that of plate boundary and crystalline layer. The activation energies (E _a) for DC-conductance in grain boundary, plate boundary and crystalline layer are 0.68 eV, 0.89 eV and 0.89 eV, respectively. Relaxation activation energies calculated from impedance plots showed similar values, 0.81 eV and 0.80 eV for crystalline layer and plate boundary, respectively. These activation energy values are found to be consistent with the E _a value of oxygen vacancies in perovskite materials. A mechanism is offered to explain the generation of oxygen vacancies in BLT ceramic and its role in temperature dependence of DC-conductance study.      

Near-infrared broadband luminescence in Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript> binary glass system

Near-infrared broadband luminescence from 1100 to 1600 nm was observed in Bi₂O₃-GeO₂ binary glasses. The strongest emission can be observed with 30 mol % Bi₂O₃ when pumped at 808 nm. The lifetimes of all samples are longer than 200 μs. The glass network was studied by Raman spectra and Bi⁺ ions are proposed as the infrared luminescence centers in this glass system. Thermal treatment in air results in partly oxidation of Bi⁺ to Bi²⁺.     

Microstructures and impedance studies of Bi<Subscript>3.15</Subscript>Nd<Subscript>0.85</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Microstructures and impedance characteristics of chemical-solution-derived Bi_3.15Nd_0.85Ti₃O₁₂ thin films were studied as functions of temperature. A dielectric anomaly was found at around 450°C, corresponding to the paraelectric to ferroelectric transition. Via complex impedance studies, grain and grain boundary contributions to the impedance were separated. The resistance of grain and grain boundaries is found governed by the same kind of space charge with an activation energy around 1.1 eV, close to that of oxygen vacancies in perovskite ferroelectrics. The low temperature ac conductance of BNdT thin films shows a frequency dispersion, which can also be ascribed to space charges mainly due to oxygen vacancies. The results were compared with SrBi₂Ta₂O₉ in terms of oxygen vacancy conductivity.     

Dielectric properties,ionic conductivity and phase transitions in La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

The dspersion dielectric permeability and ion conductivity of La₂Mo₂O₉ ceramics was studied. It was established that the observed low-frequency dielectric dispersion is due to relaxation effects related to high ion conductivity. It is shown that the phase transition in La₂Mo₂O₉ has characteristic features of a superionic phase transition.     

Ferroelectric phase transition of Nb-doped Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ceramics

Bi_3.25La_0.75Ti_3-yNb_yO₁₂ (y=0.0, 0.03, 0.09, 0.15, 0.21) were synthesized using the solid-state reaction method. The effects of Nb doping on ferroelectric properties were studied through dielectric and P-E measurements. The value of P_r increases with increasing Nb content. Bi_3.25La_0.75Ti_3-yNb_yO₁₂ ceramics exhibit a maximum remanent polarization of P_r=27 μC/cm² at an Nb content of y=0.09. These results indicate that Nb doping can improve the ferroelectric properties of BLT ceramics. The Curie temperature, T_c, decreased with increasing Nb-content, and the ferroelectric phase transition of BLTNy is a second-order transition without thermal hysteresis. PACS 77.55.+f; 77.80.-e; 77.22.Jp     

Dielectric properties of Bi<Subscript>2</Subscript>PbNb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics prepared by different techniques

Different techniques for the synthesis of Bi₂PbNb₂O₉, namely the mixed oxide technique, molten salt synthesis, hydrothermal synthesis, co-precipitation and the tartaric acid gel method were investigated and the results on the dielectric properties are reported. The heat-treatment of the precursor powders was the same for all precursor powders. Sintering at 1040 °C under ambient pressure resulted in polycrystalline specimens, while hot-forging at 1040 °C with a pressure of 20 MPa produced c-axis aligned samples. Phase composition and crystallite orientation of the sintered bodies were analyzed by X-ray diffraction. Single-phase material was obtained in all cases. Hot-forging not only yielded c-axis orientation, but also increased the relative densities above 99.4%. The relative permittivity decreased for c-axis oriented material compared to polycrystalline ceramics. Values for the relative permittivity for the hot-forged specimens at 100 °C at 100 kHz varied between 165 and 250, depending on the fabrication method. The Curie temperature for the c-axis aligned samples was 568 °C, independent of the nature of the precursor powders. PACS 77.22.-d; 77.84.-s     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Suppression of superconductivity in layered Bi<Subscript>4</Subscript>O<Subscript>4</Subscript>S<Subscript>3</Subscript> by Ag doping

We report X-ray diffraction, magnetization and transport measurements for polycrystalline samples of the new layered superconductor Bi_4?x Ag _x O₄S₃(0 ≤ x ≤ 0.2). The superconducting transition temperature (T _C) decreases gradually and finally suppressed when x < 0.10. Accordingly, the resistivity changes from a metallic behavior for x < 0.1 to a semiconductor-like behavior for x > 0.1. The analysis of Seebeck coefficient shows there are two types of electron-like carriers dominate at different temperature regions, indicative of a multiband effect responsible for the transport properties. The suppression of superconductivity and the increased resistivity can be attributed to a shift of the Fermi level to the lower-energy side upon doping, which reduces the density of states at E _F. Further, our result indicates the superconductivity in Bi₄O₄S₃ is intrinsic and the dopant Ag prefers to enter the BiS₂ layers, which may essentially modify the electronic structure.     

On synthesis of BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript>, SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript>, and PbFe<Subscript>12</Subscript>O<Subscript>19</Subscript> hexagonal ferrite ceramics with multiferroid properties

We analyze the possibility of obtaining M-type hexagonal ferrites of barium, strontium, and lead with multiferroid properties with the help of ceramic technology. Using the modified ceramic technology (especially pure initial raw materials, admixture of B₂O₃, and sintering in the oxygen atmosphere), we obtained for the first time the BaFe₁₂O₁₉ and SrFe₁₂O₁₉ samples with intense multiferroid properties at room temperature. At the same time, the employed technology does not make it possible to obtain PbFe₁₂O₁₉ samples exhibiting ferroelectricity. The multiferroid characteristics of experimental samples are compared with the characteristics of classical high-temperature multiferroic BiFeO₃ and with the characteristics of BaFe₁₂O₁₉, SrFe₁₂O₁₉, and PbFe₁₂O₁₉ ferrite ceramics obtained in accordance with polymer precursor technology. We propose a mechanism explaining multiferroid properties of the hexagonal ferrite ceramic samples and note the importance of our results for applications.     

Preparation and electrical properties of Bi<Subscript>3.25</Subscript>Pr<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films

Bi_3.25Pr_0.75Ti₃O₁₂ (BPT) ferroelectric thin films have been prepared by chemical solution deposition on platinized Si substrates. Well-crystallized BPT films can be achieved by 600 °C rapid thermal annealing. The film surface is smooth and crack-free, composed of uniform spherical grains around 90–100 nm in diameter. The electrical properties of Pt/BPT/Pt thin film capacitors were characterized by hysteresis and impedance measurements. The remanent polarization of 700 °C annealed BPT films is around 20 C/cm² at 120-kV/cm stimulus field. The dielectric constant is around 380 at 10 kHz, 100-mV amplitude. The remanent polarization of BPT film showed a slight reduction, 10% of its original value, after 2.8×10⁹ cycles, while a 30% reduction of non-volatile polarization was observed. PACS 81.15.-z; 77.55.+f; 77.22.Gm     

Low-temperature formation of thermal and electrodynamic states in Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>CaCu<Subscript>2</Subscript>O<Subscript>8</Subscript>

The formation of thermal and electrodynamic states in Bi₂Sr₂CaCu₂O₈ under the condition of current input is studied. The analysis is carried out for partial and complete current penetration under the assumption that the superconductor is cooled down to liquid helium temperature at the zero time. When the current input is continuous, the temperature dependence of the Bi₂Sr₂CaCu₂O₈ specific heat influences the form of the I-V and I-T characteristics of the superconductor. This effect is observed at high electric fields when both stable and unstable states form. As a result, the nonstationary I-V characteristic of Bi₂Sr₂CaCu₂O₈ has the only branch the slope of which is positive and decreases with increasing temperature. Therefore, the higher the rate of current input, the more pronounced the decrease in the slope. It is concluded that one cannot find the current above which instability develops from the Bi₂Sr₂CaCu₂O₈ I-V characteristic if the current input is continuous.