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.     

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.     

Synthesis, characterization and dielectric properties of europium-doped barium titanate nanopowders

Europium-doped cubic barium titanate (BT) nanocrystals with % [Eu/Ti] mol ratio varying from 0.05 to 0.25 were prepared through hydrothermal route. The nano nature of these powders was confirmed by XRD and TEM studies. Pellets were prepared after calcining the powders at 1000 °C for 2 h. These pellets were annealed at 200, 500, 700 and 1000 °C for 2 h at each temperature and used for dielectric measurements. Raman spectra of two typical pellets with %[Eu/Ti] Eu/Ti mol ratios of 0.15 and 0.25 showed all the peaks characteristic of tetragonal BaTiO₃. Pure BT showed a low dielectric constant (DC) with a value of 398. Doping with small amounts of Eu resulted in many fold increase of DC values. A maximum value of 10576 at 1 KHz frequency was observed for the sample with % [Eu/Ti] mol ratio of 0.15. Lowering of Curie temperature T_c (95 to 110 °C) was observed for pure as well as Eu-doped barium titanate.     

UV-visible spectra of perovskite iron-doped Ba0.72Sr0.28TiO3

The ultraviolet-visible spectra of the pure barium strontium titanate (Ba_0.72Sr_0.28TiO₃) and the Fe³⁺-doped Ba_0.72Sr_0.28TiO₃ were measured. The pure barium strontium titanate exhibited an ultraviolet (UV) absorption effect. The addition of Fe₂O₃ resulted in an increase of absorption wavelength. This red-shift effect was very strong even though the amount of Fe³⁺ was very small. The similar phenomenon was also observed in pure BaTiO₃ and Fe³⁺-doped BaTiO₃. The UV-absorption behavior was discussed in terms of Fe³⁺ replacing Ti⁴⁺ in the titanate with perovskite structure.     

Photocatalysis and characterization of the gel-derived TiO2 and P-TiO2 transparent thin films

The gel-derived TiO₂ and P-TiO₂ transparent films coated on fused-SiO₂ substrates were prepared using a spin-coating technique. Effects of phosphorus dopants and calcination temperature on crystal structure, crystallite size, microstructure, light transmittance and photocatalytic activity of the films were investigated. By introducing P atoms to Ti-O framework, the growth of anatase crystallites was hindered and the crystal structure of anatase-TiO₂ could withstand temperature up to 900 °C. The photocatalytic activities of the prepared films were characterized using the characteristic time constant (τ) for the photocatalytic reaction. The titania film with a smaller τ value possesses a higher photocatalytic ability. After exposing to 365-nm UV light for 12 h, the P-TiO₂ films calcined between 600 °C and 900 °C can photocatalytically decomposed ≥ 84 mol% of the methylene blue in water with corresponding τ ≤ 7.1 h, which were better than the pure TiO₂ films prepared at the same calcination temperature.     

Properties of TiO2 prepared by acid treatment of BaTiO3

TiO₃ powders were prepared by acid treatment of BaTiO₃ and their properties were investigated. The BaTiO₃ powder was subjected to HNO₃ in concentrations ranging from 10⁻³ to 8 M at 90 °C for 0.5-6 h. Dissolution of BaTiO₃ and precipitation of TiO₂ occurred at acid concentrations of 2-5 M. BaTiO₃ dissolves completely to form a clear solution at reaction times of 0.5-1 h, but a rutile precipitate is formed after 2 h of acid treatment. By contrast, anatase is precipitated by adjusting the pH of the clear solution to 2-3 using NaOH or NH₄OH solution. The rutile crystals were small and rod-shaped, consisting of many small coherent domains connected by grain boundaries with small inclination angles and edge dislocations, giving them a high specific surface area (S_BET). With increasing HNO₃ concentration, the S_BET value increased from 100 to 170 m²/g while the crystallite size decreased from 25 to 11 nm. The anatase crystals obtained here were very small equi-axial particles with a smaller crystallite size than the rutile and S_BET values of about 270 m²/g (higher than the rutile samples). The photocatalytic activity of these TiO₂ was determined from the decomposition rate of Methylene Blue under ultraviolet irradiation. Higher decomposition rates were obtained with larger crystallite sizes resulting from heat treatment. The maximum decomposition rates were obtained in samples heated at 500-600 °C. The photocatalytic activity of the TiO₂ was found to depend more strongly on the sample crystallite size than on S_BET.     

Fabrication of porous TiO2 film via hydrothermal method and its photocatalytic performances

Porous anatase (TiO₂) films were fabricated onto stainless steel substrates with Ti(OC₄H₉)₄ as a precursor via hydrothermal process. The crystallization and porous structure of TiO₂ film were dependent on the time and temperature of the hydrothermal reaction. A TiO₂ film with orderly porous structure and high crystallization was obtained upon treatment at 150 °C for 2 h. The grain size of TiO₂ is ca. 6 nm, and pore diameter is ca. 10 nm. Diffusion of Fe into the porous TiO₂ film occurred; Fe also diffused onto the surface of the film with the extension of hydrothermal reaction time or increase of the reaction temperature. The diffusion reaction has a large effect on the formation of porous TiO₂ film as well as its interface texture. However, it does not change the crystal phase of the TiO₂. The resultant TiO₂ film showed high photocatalytic activity towards degradation of gaseous formaldehyde.     

Preparation and photocatalytic activity of anatase TiO2 nanocrystallites with high thermal stability

Anatase TiO₂ nanocrystallites were prepared from TiCl₄ with addition of aqueous ammonia by changing Ti(OH)₄ hydrogel into its corresponding alcogel followed by supercritical drying in ethanol medium. The as-prepared TiO₂ was characterized by XRD, TG and BET. The results show that the prepared anatase TiO₂ has remarkable high thermal stability. The anatase structure of the prepared TiO₂ is maintained even after calcination up to temperatures as high as 800 °C. The photocatalytic activity of the prepared TiO₂ calcined at 800 °C in degradation of reactive brilliant red X-3B is comparable to commercially available nanosized P25 TiO₂.     

Nanoporous TiO2 thin film based conductometric H2 sensor

Nanoporous titanium dioxide (TiO₂) based conductometric sensors have been fabricated and their sensitivity to hydrogen (H₂) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs). Nanoporous TiO₂ films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt) NH₄F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to convert the remaining Ti into TiO₂. The scanning electron microscopy (SEM) images revealed that the average diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor responded with a highest sensitivity of 1.24 to 1% of H₂ gas at 225 °C.     

Variable temperature in situ X-ray diffraction study of mechanically activated synthesis of calcium titanate, CaTiO3

The effect of mechanical activation on formation of calcium titanate (CaTiO₃) from calcined mixtures of CaCO₃ and TiO₂ was studied by monitoring the course of this solid-state reaction by variable temperature in situ X-ray diffraction (XRD) experiments, scanning electron microscopy (SEM) and dilatometry. Two equimolar mixtures of powdered CaCO₃ and TiO₂ were prepared: one was mechanically activated by grinding in a high energy vibro-mill. A total of 32 X-ray diffraction data sets for each sample, collected between 30 and 1100 °C, were analyzed by multiphase Rietveld refinement. Quantitative phase analysis and microstructure analysis obtained from X-ray diffraction are correlated to results of scanning electron microscopy and dilatometry. In the non-activated sample, small quantities of the reactants remain in the product until 1100 °C. In the activated sample, the reaction results in pure CaTiO₃ at 920 °C.     

Preparation of monodispersed spherical barium titanate particles

Spherical barium titanate particles with cubic phase were synthesized by a low-temperature hydrothermal reaction. Firstly, The method of hydrolysis of titanium tetrachloride was used for producing spherical TiO₂ particles (0.45–1.5 μ m) with various concentrations of TiCl₄(0.05–0.2 M) and volume ratios of acetone to water solutions (RH = 0–4). These TiO₂ particles were converted to barium titanate by a hydrothermal conversion in a barium hydroxide solution. The size and morphology of the TiO₂ particles was controlled by the volume ratio of acetone to water (RH ratio) in the mixed solvent. At the RH ratio of 3, the morphology of TiO₂ particles was very uniform and discrete. These TiO₂ particles were in the anatase phase and were converted to the rutile phase when the calcination temperature increased to 700∘C and above. Uniform and spherical barium titanate particles were successfully synthesized from the as-prepared TiO₂ particles by using a hydrothermal reaction in a barium hydroxide solution. The Ba/Ti ratios, reaction temperature, and reaction time did not influence the size and morphology of BaTiO₃ particles, but increased the concentration of unfavorable salts such as Ba(OH)₂ and BaCO₃. The high purity BaTiO₃ particles could be obtained by washing with formic acid to remove the unfavorable salts. The size and morphology of the BaTiO₃ particles remained the same as those of the TiO₂ particles, confirming the in-situ transformation mechanism for the conversion of TiO₂ to BaTiO₃. The as-synthesized particles were cubic phase and transformed to tetragonal phase after calcinations at 1150∘C for 1 h. The mean density of the pellets sintered at 1300∘C for 2 h was 5.86 g/cm³ and accounted for 97.34% of the theoretical density.     

Preparation of polycrystalline BaTi2O5 by pressureless sintering

Polycrystalline BaTi₂O₅ (BT₂) was prepared by pressureless sintering in air using BaCO₃ and TiO₂ as starting materials. XRD results of the calcined powder showed BaCO₃ and TiO₂ reacted completely after being calcined above 950 °C, showing a mixture of BaTiO₃ (BT), BT₂, BaTi₄O₉ and Ba₄Ti₁₃O₃₀. A small amount of ZrO₂ (less than 0.1 wt%) was effective to prepare BT₂ in a single phase and the second phase of BT and B₆T₁₇ increased with ZrO₂ content. BT₂ sintered body in a single phase was obtained at 1175-1300 °C when ZrO₂ content was 0.08 wt%. The maximum permittivity of BT₂ sintered body was 340 at the Curie temperature (T_c) of 463 °C and the frequency of 100 kHz.     

Ultrasonic spray pyrolysis of surface modified TiO2 nanoparticles with dopamine

Spherical, submicronic TiO₂ powder particles were prepared in the low temperature process of ultrasonic spray pyrolysis (150 °C) by using as a precursor aqueous colloidal solutions consisting of surface modified 45 Å TiO₂ nanoparticles with dopamine. Detailed structural and morphological characterization of colored submicronic TiO₂ spheres was performed by X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), laser particle size analysis and FTIR techniques. Also, optical characterization of both dopamine-modified TiO₂ precursor nanoparticles and submicronic TiO₂ powder particles was performed using absorption and diffuse reflectance spectroscopy, respectively. A significant decrease of the effective band gap (1.9 eV) in dopamine-modified TiO₂ nanoparticles compared to the band gap of bulk material (3.2 eV) was preserved after formation of submicronic TiO₂ powder particles in the process of ultrasonic spray pyrolysis under mild experimental conditions. Due to the nanostructured nature, surface-modified assemblage of TiO₂ nanoparticles preserved unique ability to absorb light through charge transfer complex by photoexcitation of the ligand-to-TiO₂ band, conventionally associated with extremely small TiO₂ nanoparticles (d < 20 nm) whose surface Ti atoms, owing to the large curvature, have penta-coordinate geometry.     

Synthesis of highly-active single-crystalline TiO2 nanorods and its application in environmental photocatalysis

Highly-active anatase TiO₂ nanorods have been successfully synthesized via a simple two-step method, hydrothermal treatment of anatase/rutile titanium dioxide nanoparticle powder in a composite-hydroxide eutectic system of 1:1 M KOH/NaOH, followed by acid post-treatment. The morphology and crystalline structure of the obtained nanorods were characterized using XRD, TEM, SEM/EDX and BET surface area analyzer. The obtained TiO₂ nanorods have a good crystallinity and a size distribution (about 4-16 nm); with the dimensions of 200-300 nm length and of 30-50 nm diameter. Compared with its precursor anatase/rutile TiO₂ nanoparticles and the titanate nanotubes, the pure anatase TiO₂ nanorods have a large specific surface area with a mesoporous structure. The photocatalytic performance of the prepared nanorods was tested in the degradation of the commercial Cibacrown Red (FN-R) textile dye, under UV irradiation. Single-crystalline anatase TiO₂ nanorods are more efficient for the dye removal.     

Factors affecting CO oxidation over nanosized Fe2O3

Nanocrystallite iron oxide powders with different crystallite sizes were prepared by co-precipitation route. The prepared powders with crystallite size 75, 100 and 150 nm together with commercial iron oxide (250 nm) were tested for the catalytic oxidation of CO to CO₂. The influence of different factors as crystallite size, catalytic temperature and weight of catalyst on the rate of catalytic reaction was investigated using advanced quadrupole mass gas analyzer system. It can be reported that the rate of conversion of CO to CO₂ increased by increasing catalytic temperature and decreasing crystallite size of the prepared powders. The experimental results show that nanocrystallite iron oxide powders with crystallite size 75 nm can be recommended as a promising catalyst for CO oxidation at 500 °C where 98% of CO is converted to CO₂. The mechanism of the catalytic oxidation reaction was investigated by comparing the CO catalytic oxidation data in the absence and presence of oxygen. The reaction which was found to be first order with respect to CO is probably proceeded by adsorption mechanism where the reactants are adsorbed on the surface of the catalyst with breaking OO bonds, then CO pick up the dissociated O atom forming CO₂.     

Effect of the crystallinity of BaTiO<Subscript>3</Subscript> powders prepared using the merker method on the properties of PTCR ceramics

Barium titanate powders differing in particle size (110–740 nm) were prepared by calcining barium titanyl oxalate precipitated by the Merker method. The powders were sintered to produce PTCR ceramics with the composition 100(Ba_0.89Ca_0.08Pb_0.03)TiO₃ + ^0.8TiO₂ + ^0.7Y + ^0.1Mn + ^2.5SiO₂ and electrical properties of the ceramics were studied. The results demonstrate that improving the crystallinity of the barium titanate powder suppresses recrystallization of the ceramics and has a significant effect on their resistance ratio and electric strength. We found the optimal range of calcination temperatures (950–1000°C) for barium titanyl oxalate which ensures the highest electric strength of thermistors with a resistance of 31 Ω. The average crystallite size of the parent barium titanate powder is ∼250–320 nm.     

Effect of Cu dopant on microstructure and phase transformation of ZnTiO3 thin films prepared by radio frequency magnetron sputtering

Cu doped zinc titanate (ZnTiO₃) films were prepared using radio frequency magnetron sputtering. Subsequent annealing of the as-deposited films was performed at temperatures ranging from 600 to 900 °C. It was found that the as-deposited films were amorphous and contained 0.84 at.% Cu. This was further confirmed by the onset of crystallization that took place at annealing temperatures 600 °C. The phase transformation for the as-deposited films and annealed films was investigated in this study. The results showed that Zn₂Ti₃O₈, ZnTiO₃, and TiO₂ can coexist at 600 °C. When annealed at 700 °C, the results revealed that mainly the hexagonal ZnTiO₃ phase formed, accompanied by minority amounts of TiO₂ and Zn₂Ti₃O₈. Unlike pure zinc titanate films, this result showed that the Zn₂Ti₃O₈ phase can be stable at temperatures above 700 °C. Moreover, Cu addition in zinc titanate thin film could result in the decomposition of hexagonal (Zn,Cu) TiO₃ phase at 800 °C. When the Cu content was increased in zinc titanate thin films from 0.84 at.% to 2.12 at.%, there were only two phases; Zn₂Ti₃O₈ and ZnTiO₃, coexisting at temperatures between 700 and 800 °C. This result indicated that a greater presence of Cu dopants in zinc titanate thin films leads to the existence of the Zn₂Ti₃O₈ phase at higher temperatures.     

Effect of oxygen vacancies on ferroelectric behavior of Na1/2Bi1/2TiO3–BaTiO3 single crystals

One of the important lead-free ferroelectric solid solutions, sodium bismuth titanate–barium titanate Na_1/2Bi_1/2TiO₃–BaTiO₃ (NBT–BT) was grown by the conventional flux technique. In order to study the role of oxygen vacancies on the dielectric/ferroelectric properties, some of the crystal samples oriented along (0 0 1) and (1 0 0) planes were subjected to oxygen and nitrogen annealing processes to create different concentrations of oxygen vacancies in the samples. Dielectric and its loss measurements were carried out to analyze the role of oxygen vacancies and their corresponding dielectric behavior on NBT–BT crystals. Electron energy loss spectrum (EELS) has revealed that increasing oxygen vacancies has reduced oxidation states of Ti. X-ray rocking curve analysis has confirmed the degradation in the structural quality also on increasing the oxygen vacancies.     

Formation and transformation of ZnTiO3 prepared by sputtering process

Zinc titanate (ZnTiO₃) films were prepared using RF magnetron sputtering at substrate temperatures ranging from 30 to 400 °C. Subsequent annealing of the as-deposited films was performed at temperatures ranging from 600 to 900 °C. It was found that all as-deposited films were amorphous, as confirmed by XRD. This was further confirmed by the onset of crystallization that took place at annealing temperatures 600 °C. The phase transformation for the as-deposited films and annealed films were investigated in this study. The results revealed that pure ZnTiO₃ (hexagonal phase) can exist, and was obtained at temperatures between 700 and 800 °C. However, it was found that decomposition from hexagonal ZnTiO₃ to cubic Zn₂TiO₄ and rutile TiO₂ took place with a further increase in temperature to 900 °C.     

Dielectric properties of Y2O3 donor-doped Ba0.8Sr0.2TiO3 ceramics

Ba_0.8Sr_0.2TiO₃ ceramics doped with Y₂O₃ from 0 to 0.10 mol% exhibit normal ferroelectric phase transition, while the ceramics doped with Y₂O₃ from 0.20 to 0.30 mol% show a giant dielectric constant behavior with loss less than 0.15 at 1 kHz from −40 °C to 140 °C, which is suggested due to semiconductive grain and the Maxwell–Wagner effect by structure disordering in grain boundary. The analyses of unipolar charge for the semiconductive grain indicate three kinds of dielectric processes: thermally stimulated process of unipolar hopping, dispersion process of dielectric constant with frequency, and phase transition process accompanied with disappearance of giant dielectric constant in cubic phase. The XPS results confirm that some of the barium ions are in low energy state to form e-Ba²⁺ and to provide hopping sites for electrons. The ceramics doped with Y₂O₃ from 0.50 to 0.75 mol% recover the normal ferroelectricity. The possible mechanics are relevant to binding effect of cation vacancies on electrons.