The Influence of the Precursor on the Formation of Bi2O3 Polymorphs in CSD‐Derived Thin Films

This work examines the synthesis and characterization of crack‐free, β‐Bi₂O₃ thin films prepared on Pt/TiO₂/SiO₂/Si or corundum substrates using the sol‐gel method. We observed that the Bi‐based precursor has a pronounced influence on the β‐Bi₂O₃ phase formation. Well‐crystallized, single β‐Bi₂O₃ thin films were obtained from Bi‐2ethylhexanoate at a temperature of 400°C. In contrast, thin films deposited from Bi‐nitrate and Bi‐acetate resulted in non‐single Bi₂O₃ phase formation. TEOS was used for the stabilization of the β‐Bi₂O₃ phase. The phase composition of the thin films was characterized by means of X‐ray diffraction (XRD), whereas the morphology and thickness of the thin films were studied using scanning electron microscopy (SEM). The β‐Bi₂O₃ films' dielectric properties were characterized utilizing microwave‐frequency measurement techniques: (1) the split‐post dielectric resonator method (15 GHz) and (2) the planar capacitor configuration (1–5 GHz). The dielectric constant and dielectric loss measured at 15 GHz were 257 and 7.5 × 10^?3, respectively.     

Visible Light Photocatalytic Activity of Bismuth Ferrites Tuned by Bi/Fe Ratio

Pure perovskite BiFeO₃, sillenite Bi₂Fe₄O₉, and BiFeO₃/Bi₂Fe₄O₉ were synthesized facilely by controlling the precursor Bi/Fe ion ratio through a hydrothermal method. The phase composition, morphology, optical properties, and photocatalytic activity of as‐prepared samples were investigated in detail. Our results indicate that the morphology and properties of products strongly dependent on the precursor Bi/Fe ion ratio. Photocatalysis of Congo Red reveals that sillenite Bi₂Fe₄O₉ shows superior activity to perovskite BiFeO₃, and BiFeO₃/Bi₂Fe₄O₉ exhibited higher activity with 71.45% degradation rate in 90 min. It provides an easy and efficient way to tune the composition and photocatalytic activity of Bi‐based oxides.     

Synthesis,structural characterization,and photocatalytic activity of Bi‐based nanoparticles

Bi‐based nanoparticles were successfully synthesized (500°C/2 h) following two intermediate‐temperature routes, Pechini and a combined method of mechanical milling/molten salts. Herein, α‐Bi₂O₃/Bi₂O₂CO₃ heterostructures were identified. These types of heterostructures have shown advantages to improve the visible light responsive activity of Bi‐based nanoparticles to facilitate the separation of photogenerated electron‐hole pairs. By fixing the experimental parameters, the synthesis route and Ag contents showed to play a very important role in the phase composition of the Ag‐containing samples; the formation of Bi/Ag‐Bi₂O₃/Bi₂O₂CO₃ and Ag/Ag‐Bi₂O₃/Bi₂O₂CO₃ complex hybrid structures were revealed. The α‐Bi₂O₃/Bi₂O₂CO₃ heterostructure prepared by combined method exhibited higher photocatalytic efficiency (66.84%) for degrading methylene blue (MB) depending on Bi₂O₂CO₃ component proportion. For the Ag‐containing hybrid structures, the performance of their catalytic activity did not show an increase with respect to α‐Bi₂O₃/Bi₂O₂CO₃. However, in these samples, the degradation efficiency was slightly enhanced with the efficient doping of Ag into the α‐Bi₂O₃ structure and the existence of Bi when the Pechini method was used. Also, a possible photocatalytic process for degrading MB is presented.     

High‐temperature piezoelectric properties of 0‐3 type CaBi4Ti4O15:x wt%BiFeO3 composites

The 0‐3 type CaBi₄Ti₄O₁₅:30 wt%BiFeO₃ composite shows much better high‐temperature piezoelectric properties than the single‐phase CaBi₄Ti₄O₁₅ or BiFeO₃ ceramics. The composite with 0‐3 type connectivity exhibits a high density of 7.01 g/cm³, a saturated polarization of 21.5 μC/cm² and an enhanced piezoelectric d₃₃ of 25 pC/N. After the poled composite was annealed at 600°C, its d₃₃ is 21 pC/N at room temperature. Resistance of the composite decreases slowly from 10⁹ ohm at 20°C to ~10⁵ ohm at 500°C. Furthermore, the poled composite shows strong radial and thickness dielectric resonances at 20°C‐500°C.     

Effects of precursor chemistry and thermal treatment conditions on obtaining phase pure bismuth ferrite from aqueous gel precursors

Phase pure BiFeO₃ powders are synthesized by an entirely aqueous solution–gel route, starting from water soluble Fe(III) nitrate or citrate, and Bi(III) citrate as precursors. In order to obtain stable solutions, which transform to homogeneous gels upon drying, the pH is adjusted to 7 and a citric acid content equimolar to the metal ions is selected.The presence of nitrate strongly accelerates the thermo-oxidative decomposition step of the precursor gel around 200 °C, and the decomposition is finished at a lower temperature for the nitrate containing precursor (460 °C) than without nitrates (500 °C) in dynamic dry air. An oxidative ambient is required to fully decompose the precursor.The presented synthesis allows very low temperature (400 °C) crystallization of BiFeO₃ together with a secondary phase, as shown by high temperature XRD. This parasitic phase remains up to high temperatures, where decomposition of BiFeO₃ is observed from 750 °C onwards, and Bi₂Fe₄O₉ is formed. However, optimization of the furnace treatment, considering anneal temperatures and heating rates showed that phase pure BiFeO₃ can be obtained, with the heating rate being the crucial factor (5 °C/min). The chemical purity of the powders is confirmed by FTIR, and the antiferromagnetic to paramagnetic phase transition is demonstrated by DSC measurements.     

Preparation and electrical properties of ZnO‐Bi2O3‐based multilayer varistors with base metal nickel inner electrodes

In this study, ZnO‐Bi₂O₃‐based multilayer varistors (MLVs) cofired with nickel (Ni) inner electrodes were prepared by tape‐casting method. Samples were sintered in pure nitrogen (N₂) to keep Ni from being oxidized, and then reoxidized in air to obtain the nonlinear properties (reduction‐reoxidation method). The EDAX results showed that Ni inner electrodes are stable and have no evident migration into ZnO‐Bi₂O₃‐based ceramics when sintered in N₂. The influence of reoxidation temperature on microstructures and nonlinear properties of samples were studied. Samples reoxidized at the temperatures lower than 650°C showed poor nonlinear properties. After reoxidized in air at 700°C for 2 hours, samples exhibited nonlinear properties of V_1 mA=16.3 V, α=26.5, I_L=0.68 μA. At the reoxidation temperature higher than 750°C, the oxidation of Ni inner electrodes deteriorated the nonlinear properties of samples. It demonstrated that ZnO‐Bi₂O₃‐based MLVs with base metal Ni inner electrodes proposed in this work are suitable for reduction‐reoxidation method. The replacement of noble metals Pt or Ag/Pd alloys by base metal Ni is expected to lower the cost of ZnO‐Bi₂O₃‐based MLVs.     

Luminescent oxide materials obtained by the extraction pyrolytic method

Luminescent Y_1.74Eu_0.16Bi_0.1O₃ films have been obtained by extraction pyrolytic method. The formation of a crystalline structure in the film upon isothermal annealing in air at 600?C650°C was established by X-ray diffraction. Single-phase Y_1.74Eu_0.16Bi_0.1O₃ films begin to exhibit luminescent properties after pyrolysis at 500°C; the intensity of luminescence increases with increasing temperature. The films annealed at 800°C consists of defect-free homogeneous crystallites with sizes of about 0.7 ??m and demonstrats high luminescence intensity.     

Electrical properties of bismuth ferrites: Bi2Fe4O9 and Bi25FeO39

Bi₂Fe₄O₉ was prepared by solid-state reaction and the electrical properties measured by impedance spectroscopy. After annealing in O₂ at 900 °C, Bi₂Fe₄O₉ is an electrically-homogeneous insulator. Its high frequency permittivity is constant (∼14.1) over the temperature range 300–400 °C and shows no evidence of incipient ferroelectricity at lower temperatures. On annealing in N₂ at 900 °C, the pellets gradually decompose.Bi₂₅FeO₃₉ was prepared by both solid-state reaction and mechanosynthesis. It showed a modest amount of mixed conduction of both oxide ions and holes. Impedance analysis showed a complex response that best fitted an equivalent circuit consisting of a parallel combination of long-range conduction and short range dielectric relaxation elements.The electrical conductivity of both Bi₂Fe₄O₉ and Bi₂₅FeO₃₉ is less than that of BiFeO₃ prepared by solid-state reaction, which indicates that any leakage conductivity of BiFeO₃ is not due to the possible presence of small amounts of these secondary phases.     

Molten Salt Synthesis of Bismuth Ferrite Nano‐ and Microcrystals and their Structural Characterization

Bismuth ferrite nano‐ and microcrystals were prepared by a facile molten salt technique in two kinds of molten‐salt‐based systems (NaCl–KCl and NaCl–Na₂SO₄). In the NaCl–KCl salt system, a systematic study indicating the effects of process parameters (e.g., calcination temperature, holding time as well as the molten salt ratios) on the bismuth ferrite formation mechanism and structural characteristics is reported. The results show that almost pure phase BiFeO₃ powders with minimum impurity phase of Bi₂Fe₄O₉ were synthesized at temperatures of 700°C–800°C, whereas high calcination temperature (e.g., 900°C) resulted in the formation of almost pure phase Bi₂Fe₄O₉ powders. The prolonged holding time increased the particle size via the Ostwald ripening mechanism; however, there was little effect on the particle morphology. Similar phenomenon occurred as increasing the molten salt ratios. In the NaCl–Na₂SO₄ salt systems, it is found that low NP‐9 (nonylphenyl ether, NP‐9) surfactant content (0–5 mL) led to the formation of almost pure phase BiFeO₃ powders, whereas high NP‐9 surfactant content (e.g., 20 mL) resulted in pure phase Bi₂Fe₄O₉ powders. The average particle size of the BiFeO₃ powders was decreased as increasing the NP‐9 surfactant content, whereas their morphologies did not change significantly. Because of the simplicity and versatility of the approach used, it is expected that this methodology can be generalized to the large‐scale preparation of other important transitional metal oxides with controllable sizes and shapes.     

Microstructure and ferroelectric properties of Ta-doped Bi3.25La0.75Ti3O12/ZnO thin film capacitors

Ta-doped Bi_3.25La_0.75Ti₃O₁₂(BLTT)/ZnO films were fabricated on Pt(111)/Ti/SiO₂/Si substrates by a magnetron sputtering method. Firstly, ZnO crystal thin films were grown on the substrates by a reactive sputtering method. Then, BLTT thin films were deposited on the ZnO layers at room temperature and post-annealed at 600 °C. The micromorphology, ferroelectric and dielectric properties of BLTT/ZnO films were analyzed. The XRD analysis shows that ZnO buffer layer significantly reduces the crystallization temperature of BLTT thin film. The TEM results show that lamellar BLTT grains are grown on ZnO layer at a certain angle with few elements diffusion at the interface of ZnO phase and Bi₄Ti₃O₁₂ phase. The ferroelectric properties indicate that BLTT/ZnO films exhibit different remanent polarization and coercive fields under electric field with different directions. The novel mechanism of tailoring ferroelectric properties may open new possibilities for designing special ferroelectric devices.     

Comparative study of aromatization selectivity during N‐heptane reforming on sintered Pt/Al2O3 and Pt‐Re/Al2O3 catalysts

BACKGROUND: The metal dispersed over a support can be present as small crystallites with sizes less than 5 nm. The smaller crystallites favour aromatization while larger crystallites favour cracking/hydrogenolysis. Sintering results in the agglomerization of smaller metal crystallites. Correlation of size with aromatization selectivity was investigated. RESULTS: The primary products of n‐heptane reforming on fresh Pt were methane, toluene, and benzene, while on fresh Pt‐Re, the only product was methane. Both catalysts exhibited enhanced aromatization selectivity at different oxygen sintering temperatures. The reaction products ranged from only toluene at 500 °C sintering temperature to methane at a sintering temperature of 650 °C with no reaction at 800 °C for the Pt/Al₂O₃ catalyst. On Pt‐Re/Al₂O₃ catalyst, methane was the sole product at a sintering temperature of 500 °C while only toluene was produced at a sintering temperature of 800 °C. CONCLUSION: This is the first time that sintering has been used to facilitate aromatization of supported Pt and Pt‐Re catalysts. A superior selectivity behaviour associated with bi‐metallic Pt catalysts is established. It was found that no reaction occurred on Pt catalyst after sintering at 800 °C whereas sintering Pt‐Re at 800 °C promoted aromatization solely to toluene. Copyright © 2008 Society of Chemical Industry     

Sintering‐induced aromatization during n‐heptane reforming on Pt/Al2O3 catalysts

A platinum/alumina catalyst was sintered in oxygen and hydrogen atmospheres using two metal loadings of the catalyst: 0.3% Pt and 0.6% Pt. After sintering, the aromatization selectivity was investigated with the reforming of n‐heptane as the model reaction at a temperature of 500 °C and a pressure of 391.8 kPa. The primary products of n‐heptane reforming on the fresh platinum catalysts were methane and toluene, with subsequent conversion of benzene from toluene demethylation. To induce sintering, the catalysts were treated with oxygen at a flow rate of 60 mL min^?1, pressure of 195.9 kPa and temperatures between 500 and 800 °C. The 0.3% Pt/Al₂O₃ catalyst exhibited enhanced aromatization selectivity at various sintering temperatures while the 0.6% Pt/Al₂O₃ catalyst was inherently hydrogenolytic. The fact that aromatization was absent on the 0.6% Pt/Al₂O₃ catalyst was attributed to the presence of surface structures with dimensionality between two and three as opposed to essentially 2‐D structures on the 0.3% Pt/Al₂O₃ catalyst surface. On the 0.3% Pt/Al₂O₃ catalyst, the reaction product ranged from only toluene at a 500 °C sintering temperature to predominantly cracked product at a sintering temperature of 650 °C and no reaction at 800 °C. For sintering at about 650 °C, subsequent conversion of n‐heptane was complete and dropped thereafter. The turnover number was observed to change from 0.07 to 2.26 s^?1 as the dispersion changed from 0.33 to 0.09. The Koros–Nowark (K–N) test was used to check for the presence of internal diffusional incursions and Boudart's criterion was used for structural sensitivity determination. The K–N test indicated the absence of diffusional resistances while n‐heptane reforming was found to be structure sensitive on the Pt/Al₂O₃ catalyst. Copyright © 2006 Society of Chemical Industry     

Mullite interaction with bismuth oxide from minerals and sol–gel processes

Mullite compounds with bismuth oxide in the SiO₂–Al₂O₃–Bi₂O₃ ternary system were synthesized from TEOS (C₂H₅O)₄Si, aluminum nitrate Al(NO₃)₃·9H₂O and bismuth nitrate Bi(NO₃)₃. Thermal and structural transformations were studied at temperatures ranging from 1000 to 1400 °C. The coexistence of Al₄Bi₂O₉ and Bi₄Si₃O₁₂ phases at temperatures up to 1000 °C was observed in compositions containing 5–31 mol% Bi₂O₃. Mullite is observed at temperature higher than 1000 °C in composition not exceeding 5 mol% of Bi₂O₃. Corundum coexist with a liquid above 1000 °C in all compositions containing more than 5 mol% Bi₂O₃. The liquid temperature is slightly above 1000 °C for all compositions. A tentative pseudo-binary diagram mullite-Bi₂O₃ is proposed. A similar system was studied with silico-aluminate compositions containing kaolinite and muscovite minerals. The occurrence of a liquid when Bi₂O₃ is added highly favors the mullite growth at temperature below 1200 °C. It is favored by local concentrations at interfaces of a transient liquid phase, which enhance the mobility of species.     

Glass Additive Influence on the Sintering Behaviors,Magnetic and Electric Properties of Bi–Zn Co‐Doped Co2Y Ferrites

The Bi₂O₃–B₂O₃–ZnO–SiO₂ (BB35SZ) glass effects on the sintering behavior and magnetic properties of Bi–Zn co‐doped Co₂Y ferrites were investigated in developing low‐temperature‐fired ferrites. The results indicate that BB35SZ glass can be used as a sintering aid to reduce the densification temperature of Co₂Y ferrites from 1300°C to 900°C. The 2(Ba_0.9Bi_0.1O)·2(Zn_0.4Co_0.4Cu_0.2O)·6(Fe_1.97Zn_0.03O₃) ferrite with 4 wt% BB35SZ glass can be densified below 900°C, exhibiting an initial permeability of 3.4 and quality factor of 55. This process provides a promising candidate for multilayer chip magnetic devices for microwave applications.     

Effects of Ho and Ti Doping on Structural and Electrical Properties of BiFeO3 Thin Films

Effects of Ho and Ti ions individual doping and co‐doping on the structural, electrical, and ferroelectric properties of the BiFeO₃ thin films are reported. Pure BiFeO₃, (Bi_0.9Ho_0.1)FeO₃, Bi(Fe_0.98Ti_0.02)O_3+δ, and (Bi_0.9Ho_0.1)(Fe_0.98Ti_0.02)O_3+δ thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. All thin films were crystallized in distorted rhombohedral structure containing no secondary or impurity phases confirmed by using an X‐ray diffraction study. Changes in microstructural features, such as grain morphology and grain size distribution, for the doped samples were analyzed by a scanning electron microscopy. From the experimental results, a low electrical leakage (1.2 × 10^?5 A/cm² at 100 kV) and improved ferroelectric properties, such as a large remnant polarization (2P_r) of 52 μC/cm² and a low coercive field (2E_c) of 886 kV/cm, were observed for the (Bi_0.9Ho_0.1)(Fe_0.98Ti_0.02)O_3+δ thin film. Fast current relaxation and stabilization observed in the (Bi_0.9Ho_0.1)(Fe_0.98Ti_0.02)O_3+δ imply effective reduction and neutralization of charged free carriers.     

Gibbs free energy of formation of Bi2O3 from EMF cells with δ-Bi2O3 solid electrolyte

Determination of thermodynamic data on the formation of Bi₂O₃ was established by emf measurements as a function of temperature in the range 660–820°C on the system Metal, Bi(1)|Bi₂O₃|Pt, O₂. From the results using a tungsten electrode the following relation was found: ΔG⁰ = ?(134.7 ± 1.2) + (64.0 ± 1.2) × 10^?3 T kcal mole^?1 (validity range: 940–1080 K). Standard thermodynamic data at 298 K were calculated as ΔG⁰ = ?119.2 ± 2.1 kcal mole^?, ΔH⁰ = ?139.0 ± 1.2 kcal mole^?1, and ΔS⁰ = ?66.3 ± 1.2 eu.     

Development of a lead‐free copper co‐fired BNT‐based piezoceramic sintered at low temperature

Compatibility of Bi‐based piezoelectric ceramic and copper electrodes is demonstrated by co‐firing 0.88Bi_1/2Na_1/2TiO₃–0.08Bi_1/2K_1/2TiO₃–0.04BaTiO₃ (BNKBT88) with copper. A combination of Bi₂O₃, CuO, ZnO, Li₂CO₃, and B₂O₃ are used as additives to reduce firing temperature to 900°C with minimal effect on the electromechanical properties compared to sintering at 1150°C without additives. Co‐firing with copper electrodes requires controlled oxygen sintering at low temperature. The atmosphere is controlled using carbon dioxide and hydrogen gas to maintain an oxygen partial pressure of 6.1 × 10^?8 atm, which is necessary for the coexistence of Cu metal and Bi₂O₃. The thermodynamic activity of bismuth oxide in BNKBT88 is calculated to be 0.38. BNKBT88 ceramics were successfully co‐fired with internal as well as surface Cu metal electrodes. The copper co‐fired ceramics were successfully polarized and the dielectric and piezoelectric properties are evaluated.     

Effect of Concentration and Temperature on the Surface Morphology of Gd2O3 Nanocrystallites in Silica

Gd(NO₃)₃.6H₂O and TEOS were used as precursors and obtained Gd₂O₃:SiO₂ ceramic powder having different concentration of Gd₂O₃ as 2.2, 2.8, 3.4, and 4.0 wt % using solgel process. The powdered samples were annealed at 500°C and 900°C temperatures and characterized by XRD, FTIR, SEM, and TEM. In X‐ray diffraction, cubic phase of Gadolinium oxide is reported only for the annealed samples having higher concentration (3.4 & 4.0 wt %) of Gd₂O₃. SEM and TEM results further confirm that the surface morphology of the microstructures depend on the temperature and concentration.     

Structural,magnetic and optical properties of BiFeO3 synthesized by the solvent-deficient method

Bismuth ferrite (BiFeO₃, BFO) powders were synthesized by a simple and cost-effective solvent-deficient method using bismuth nitrate, iron nitrate, and ammonium bicarbonate as the only precursors. Single phase BiFeO₃ powder was fabricated after the Bi:Fe ratio was adjusted and after the precursor mixture was calcined for one hour at 600 °C. We investigated the formation reactions, crystal structure, particle size distribution, magnetic and optical properties of synthesized BiFeO₃. X-ray diffraction revealed the formation of well-crystallized BFO nanocrystallites starting at a temperature of 450 °C. BiFeO₃ powder calcined at 600 °C showed very weak ferromagnetism at room temperature which is different from the linear M–H relationship in bulk BiFeO₃ ceramics. The remnant magnetization value (Mr) was found to be 5 × 10⁻³ emu g⁻¹ and a coercive field value (Hc) nearly 500 Oe. The UV–visible spectra showed maximum adsorption at ∼464 nm with a derived bandgap value of 1.85 (1.8449 ± 0.0013) eV for BFO nanocrystallites supporting their potential application as visible light-response photocatalysts. Direct bandgap value obtained from reflectance measurement is determined to be 2.25 (2.2464 ± 0.0065) eV.     

Bi2O3 nanoparticles incorporated porous TiO2 films as an effective p‐n junction with enhanced photocatalytic activity

Porous TiO₂ films decorated with Bi₂O₃ nanoparticles are fabricated via alkali‐hydrothermal of titanium (Ti) plate by varying the reaction time. The amorphous TiO₂ is transformed into anatase after annealing the films at 500°C in air. The p‐type Bi₂O₃ nanoparticles are successfully assembled on the surface of porous n‐type TiO₂ films through the ultrasonic‐assisted successive ionic layer adsorption and reaction (SILAR) technique to form Bi₂O₃/TiO₂ nanostructure by the two cycles. The obtained Bi₂O₃/TiO₂ films are consisted of a well‐ordered and uniform porous structure with an average pore diameter of about 100‐200 nm containing homogeneously dispersed Bi₂O₃ nanoparticles of ~5 nm diameter. Moreover, the resultant composites present excellent photocatalytic performance toward methyl blue (MB) degradation under UV and visible light irradiation, which could be mainly ascribed to the enhanced light adsorption capacity of unique composite structure and the formation of p‐n heterojunctions in the porous Bi₂O₃/TiO₂ films. This research is helpful to design and construct the highly efficient heterogeneous semiconductor photocatalysts.