New Method to Prepare Nitrogen-Doped Titanium Dioxide and Its Photocatalytic Activities Irradiated by Visible Light

A Ti-based metal organic compound is taken as the precursor to be decomposed in NH₃ flow at a certain temperature to prepare modified TiO₂ with high photocatalytic activity under visible-light irradiation. The processes of doping and crystallization of TiO₂ are conducted at the same time during the treatment in the NH₃ flow. This approach could efficiently dope N into anatase TiO₂ lattice. The prepared TiO₂ also has well-defined mesoporosity with a BET area of 217 m²/g.     

Surface barrier layer effect in (In + Nb) co‐doped TiO2 ceramics: An alternative route to design low dielectric loss

Giant dielectric permittivity (ε′) with low loss tangent (tanδ) was reported in (In + Nb) co‐doped TiO₂ ceramics. Either of electron‐pinned defect‐dipole or internal barrier layer capacitor model was proposed to be the origin of this high dielectric performance. Here, we proposed an effectively alternative route for designing low‐tanδ in co‐doped TiO₂ ceramics by creating a resistive outer surface layer. A pure rutile‐TiO₂ phase with a dense microstructure and homogeneous dispersion of dopants was achieved in (In + Nb) co‐doped TiO₂ ceramics prepared by a simple sol‐gel method. Two giant dielectric responses were observed in low‐ and high‐frequency ranges, corresponding to extremely high ε′≈10⁶‐10⁷ and large ε′≈10⁴‐10⁵, respectively. After annealing in air, a low‐frequency dielectric response disappeared and could be restored by removing the outer surface of the annealed sample, indicating the dominant electrode effect in the initial sample. Annealing can cause improved dielectric properties with a temperature‐ and frequency‐independent ε′ value of ≈1.9 × 10⁴ and cause a decrease in tanδ from 0.1 to 0.035. High dielectric performance in (In_0.5Nb_0.5)_xTi_1?xO₂ ceramics can be achieved by eliminating the electrode effect and forming a resistive outer surface layer.     

Effect of dopant precursors on the optical properties of rare-earths doped oxyfluoride glass-ceramics

The crystallization of fluoride nanocrystals (NCs) in chemically and mechanically stable aluminosilicate glasses has shown interesting optical properties even for small crystal fractions (10-15 wt%). When rare-earth (RE) ions are used as dopants, crystal-like features can be reproduced and an increase in the emission and/or energy transfer processes, with respect to the starting glasses, is observed. A crucial point for these materials is the study of the local surrounding of RE ions and their incorporation in the NCs. In fact, the effective concentration in the NCs can be much higher than the nominal concentration, up to one order of magnitude or even higher. The knowledge of RE ions incorporation in the NCs permits choosing proper doping levels to optimize both linear and nonlinear optical properties. In this work, transparent oxyfluoride glass-ceramics with LaF₃ NCs, doped with Nd³⁺ and Er³⁺ using oxide and fluoride precursors, were prepared using the melt-quenching method and controlled crystallization. The local surrounding of the RE ions was studied using X-ray absorption spectroscopy, electron paramagnetic resonance and photoluminiscence. The results show that most RE ions are already in a fluorine-rich amorphous environment even in the initial glass. The crystallization process provokes the RE ion redistribution and incorporation in the fluoride NCs. The different RE precursors, used as oxides or fluorides, have an influence on the incorporation of the RE in the NCs and, as a consequence, on the final optical properties.     

Effect of the Liquid-Phase Characteristic on the Microstructures and Dielectric Properties of Donor- (Niobium) and Acceptor- (Magnesium) Doped Barium Titanate

Changes in the microstructure and dielectric properties with the variation of the donor/acceptor ratio in BaTiO₃ ceramics were investigated. In donor-rich specimens, a liquid that appeared during sintering did not penetrate into grain boundaries. However, in the acceptor-rich specimens, the grains were separated by a liquid film during sintering. The much higher mobility of the liquid film than that of the grain boundaries was suggested to cause extensive grain growth in acceptor-rich BaTiO₃. The macroscopic homogenization of dopants because of grain growth in acceptor-rich specimens resulted in changes in the dielectric properties.     

Electro‐Optic Property of Mg2+/Er3+‐Codoped LiNbO3 Crystal: Mg2+ Concentration Threshold Effect

A series of Mg²⁺/Er³⁺‐codoped congruent LiNbO₃ crystals were grown by Czochralski method from the growth melts containing 0.5 mol% Er₂O₃ while varied MgO content from 0.0 to 7.0 mol%. The unclamped electro‐optic coefficients γ₁₃ and γ₃₃ of these crystals were measured by Mach–Zehnder interferometry. Two different voltage‐applying schemes were adopted: one is the DC voltage applied to the crystal via Al films coated onto crystal surfaces and another is via a pair of external Cu slab electrodes. The coefficients measured by the two schemes show similar strong dependence on Mg²⁺ concentration. The dependence is non‐monotonous, dramatic, and unusual, and reveals the features of two Mg²⁺ concentration thresholds of optical damage: one in the Mg²⁺ concentration range of 1.2–2.0 mol% (in crystal) and another in 4.5–5.0 mol%. Around the threshold the electro‐optic coefficient decreases abruptly at first and then recovers quickly, and the coefficient drops by >20% (12%) at the first (second) threshold, which exceeds the error 3% considerably. The dramatic behavior is qualitatively explained on the basis of the EO coefficient model of LiNbO₃ and the defect structure model for Mg²⁺‐doped LiNbO₃.     

Lattice Model for Estimating the Opacity of White Coatings

White pigments impart opacity to films and coatings by virtue of their ability to scatter incident light. This study considers a homogeneous coating that contains a low concentration of randomly dispersed, monodisperse pigment particles. The optical properties are determined using a lattice model with cell size defined by the diameter ( d ) of the particles. For pure scattering, the contrast ratio (CR) is an algebraic function of the scattering coefficient (κ), pigment volume fraction (φ), and coating layer thickness ( L ), as follows: [formula omitted]When tested against literature data for white films opacified with titanium dioxide, an empirical expression with a single adjustable constant provides a better interpolation formula than the above equation. This discrepancy is attributed to the contribution of a minor amount of absorption to the measured opacity.     

Direct-Current Field Dependence of Dielectric Properties in Alumina-Doped Barium Strontium Titanate

The dielectric properties of (Ba_0.6Sr_0.4)TiO₃ and Al₂O₃-doped (Ba_0.6Sr_0.4)TiO₃ have been characterized. The grain size of the specimen is maximum for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 1 wt% Al₂O₃. The density and the real part of the relative dielectric constant each decrease as the Al₂O₃ content increases. The loss factor is minimum for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 2 wt% Al₂O₃. The dielectric constant of the specimens decreases as the applied dc field increases. The influence of the dc field on the loss factor is much less than that on the dielectric constant. The tunability is ∼24% for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 1 wt% Al₂O₃.     

Microwave Dielectric Properties of CaTiO3-CaAl1/2Nb1/2O3 Ceramics Doped with Li3NbO4

The microwave dielectric properties of CaTi_{1− x} (Al_1/2Nb_1/2) _x O₃ solid solutions (0.3 ≤ x ≤ 0.7) have been investigated. The sintered samples had perovskite structures similar to CaTiO₃. The substitution of Ti⁴⁺ by Al³⁺/Nb⁵⁺ improved the quality factor Q of the sintered specimens. A small addition of Li₃NbO₄ (about 1 wt%) was found to be very effective for lowering sintering temperature of ceramics from 1450–1500° to 1300°C. The composition with x = 0.5 sintered at 1300°C for 5 h revealed excellent dielectric properties, namely, a dielectric constant (ɛ_r) of 48, a Q × f value of 32 100 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −2 ppm/K. Li₃NbO₄ as a sintering additive had no harmful influence on τ_f of ceramics.     

Effect of Acceptor and Donor Dopants on the Dielectric and Tunable Properties of Barium Strontium Titanate

The effects of different concentrations of Mn²⁺, Mg²⁺, Al³⁺, Fe³⁺, La³⁺, and Nb⁵⁺ on the dielectric and tunable properties of Ba_0.6Sr_0.4TiO₃ ceramics were investigated. It was found that doping in small amounts with acceptor ions such as Mg²⁺, Fe³⁺, and Al³⁺ could meliorate the dielectric properties clearly. Decrease of dielectric loss was attributed to the formation of compensating defects originating from acceptor substitution. It was concluded that the tunability was linked to both the dielectric constant and the grain size. A higher figure of merit was obtained by doping the ceramics with smaller ions of Al and Fe, compared to Ti.     

Photocatalytic Activity of (Copper, Nitrogen)-Codoped Titanium Dioxide Nanoparticles

(Copper, Nitrogen)-codoped titanium dioxide (TiO₂) nanoparticles have been prepared via a sol–gel route, followed by heat treatment at an elevated temperature. Such (Cu, N)-codoped TiO₂ nanoparticles showed a strong absorption in the visible region and a red shift in the band gap transition and exhibited an enhanced photocatalytic activity as compared with the pure, N-doped and Cu-doped TiO₂ for xylenol orange decomposition.     

Dopant Effect on Local Dielectric Properties in Barium Titanate Based Electroceramics Determined by Transmission EELS

Local electronic excitations of Nb-doped BaTiO₃ electroceramic were investigated using low-loss electron energy loss (EEL) spectroscopy with a transmission electron microscope. The variations in electronic structure of the BaTiO₃ were monitored as a function of Nb content by using Kramers-Krönig analysis of the low-loss EEL spectra. We found that the valence state of Nb (+5) as compared with that of the Ti (+4) introduces changes in the valence and conduction band states of BaTi_{1− x} Nb _x O₃ samples. The real part of the dielectric function, Re(1/ɛ), displays an increasingly less negative character with higher amounts of dopant and the valence plasmon exhibits "quasi-plasmon" characteristics with the addition of Nb (at 0.0–1.8 at.%). Further, the plasmon energy shifts (by about 0.5 eV) to higher values with Nb additions. Significant changes take place in oscillator strengths of excitations in local (nanometer-scale) regions of the perovskite samples. This investigation demonstrates a method to quantitatively assess electronic properties, at the submicrometer scale, of doped ceramics used in electronic and electrooptical applications.     

Single CaO accelerated densification and microstructure control of highly transparent YAG ceramic

In this work, a small amount of CaO single dopant was adopted to realize the densification and microstructure control of fine grained YAG ceramic with excellent optical quality, by a simple solid‐state reaction and one‐step vacuum sintering method. Then, highly transparent YAG ceramics (T = 84.4% at 1064 nm) were obtained just after vacuum sintering at 1820°C for 8 hours. The average grain size was only 2.7 μm, when the total amount of CaO was as low as 0.045 wt%. The effect of CaO on the microstructural evolution and optical property of the as‐fabricated YAG ceramics was systematically investigated in detail. It was found that CaO dopant promoted both densification and grain growth of YAG ceramics when the sintering temperature was lower than 1660°C, however, it dramatically inhibited grain growth when the sintering temperature was further increased.     

Large Piezoelectricity and Ferroelectricity in Mn‐Doped (Bi0.5Na0.5)TiO3‐BaTiO3 Thin Film Prepared by Pulsed Laser Deposition

Mn‐doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (MnBNBT) thin films were prepared on SrRuO₃ (SRO)‐coated (001) SrTiO₃ (STO) single crystal substrates by pulsed laser deposition under different processing conditions. Structural characterization (i.e., XRD and TEM) confirms the epitaxial growth of STO/SRO/MnBNBT heterostructures. Through the judicious control of deposition temperature, the defect level within the films can be finely tuned. The MnBNBT thin film deposited at the optimized temperature exhibits superior ferroelectric and piezoelectric responses with remanent polarization P_r of 33.0 μC/cm² and piezoelectric coefficient d₃₃ of 120.0 ± 20 pm/V.     

Fluorine as a Donor Dopant in Barium Titanate Ceramics

We have studied the electrical properties and microstructure of fluorine-doped BaTiO₃ ceramics. The samples were prepared using a classical ceramic technology that involved the calcination of intimately mixed powders of BaCO₃, TiO₂, and BaF₂. When the samples were sintered in untreated ambient air, the fluorine from the sample reacted with water vapor and formed gaseous HF. To prevent this hydrolysis of the fluorine, we sintered the samples in dried air. The fluorine-doped BaTiO₃ ceramics sintered in a dry atmosphere showed microstructures and electrical properties typical of donor-doped BaTiO₃. The samples containing up to 0.3 mol% of fluorine were coarse-grained, semiconducting, and displayed a remarkable PTCR effect. In contrast, the samples with a higher fluorine concentration were fine grained and insulating. A SIMS elemental mapping of the samples showed that the fluorine was distributed throughout the microstructure of the semiconducting samples; however, the fluorine concentration was enriched at grain boundaries and in the BaTi₂O₅ intergranular phase.     

可见光响应型非金属掺杂TiO2的研究进展

综述了各种非金属(N、S、C、B)掺杂TiO2在可见光范围的响应,以及N和F共掺杂TiO2、N和La^3 共掺杂TiO2、B与Ni2O3复合的制备及其光催化性能的研究进展。     

Preparation, Structure, and Properties of Thermally and Mechanically Improved Aluminum Titanate Ceramics Doped with Alkali Feldspar

Aluminum titanate (AT) ceramic materials doped with alkali feldspar ((Na_0.6K_0.4)AlSi₃O₈) have been prepared. These ceramics exhibited high sinterability, large resistance to thermal decomposition, and large flexure strength. The existence of liquid-phase feldspar at sintering temperatures promoted the formation of AT ceramics as the sintering agent. It was considered that silicon ions substituting for aluminum ions at the surface of AT crystal grains lowered the surface energy and hindered the diffusion of Ti⁴⁺ and Al³⁺, giving rise to the large resistance to thermal decomposition. As a result, doping with alkali feldspar was found to effectively improve the mechanical and thermal properties of AT ceramics.     

New Hydrolytic Process for Producing Zirconium Dioxide, Tin Dioxide, and Titanium Dioxide Nanoparticles

Nanocrystalline ZrO₂, SnO₂, and TiO₂ were synthesized through a simple hydrolytic process based on the etherification of alcohols. The obtained products had good uniformity and were less aggregated than in other synthesis techniques. The synthesis of ZrO₂ and SnO₂ in this process was dependent mainly on the reaction temperature, whereas the morphologies of TiO₂ exhibited a dependence on the alcohols used.     

Origin of Microwave Dielectric Loss in ZnNb2O6-TiO2

(1− x )ZnNb₂O₆· x TiO₂ ceramics were prepared using both anatase and rutile forms of TiO₂. At a composition of x = 0.58, a mixture region of ixiolite (ZnTiNb₂O₈) and rutile was observed and the temperature coefficient of resonant frequency (τ_f) was ∼0 ppm/°C. We found that although ɛ_r and τ_f were comparable, the quality factor ( Q × f , Q ≈ 1/ tan δ, f = resonant frequency) of 0.42ZnNb₂O₆·0.58TiO₂ prepared from anatase and rutile was 6000 and 29 000, respectively. The origin of the difference in Q × f of both samples was investigated by measuring electrical conductivity and by analysis of the anatase–rutile phase transition. The anatase-derived sample had higher conductivity, which was related to the reduction of Ti⁴⁺. It is suggested that the increase of dielectric loss originates from an increase in Ti³⁺ and oxygen vacancies due to an anatase–rutile phase transition.     

Development of optical grade (TbxY1−x)3Al5O12 ceramics as Faraday rotator material

Super full dense (Tb_xY_1?x)₃Al₅O₁₂ (x=0.5‐1.0) ceramics with optical grade (pore‐free) were successfully produced by solid‐state reaction between Tb₄O₇ and Al₂O₃ raw powders. Transparent sintered bodies were obtained by sintering at 1720°C for 5 hours in vacuum furnace. By additional HIP treatment, optical scattering centers were effectively removed, and finally the optical quality of the sintered bodies was improved to optical grade. Optical loss of the obtained samples at 1064 nm was approximately 0.1%/cm, and optically inhomogeneous parts were not observed inside the materials. Gaussian mode laser beam quality was not deteriorated after passing through the sample. Transmitted wavefront distortion inspected by interferometry was as excellent as λ/12. Verdet constant increased with an increase of Tb content in the garnet composition. When x=1.0, the Verdet constant was 307, 196, and 60 rad T^?1 m^?1 for 532, 633, and 1064 nm, respectively, at each measuring wavelength. These values were about 1.5 times higher than that of the commercially available TGG (Tb₃Ga₃O₁₂) crystal. Insertion loss of the produced (Tb_0.6Y_0.4)₃Al₅O₁₂ and TAG ceramics at 1064 nm was 0.01 and 0.05 dB, respectively, and extinction ratio was 39.5 and 40.3 dB, respectively. These properties were superior to that of the commercial high‐quality TGG single crystal (insertion loss: 0.05 dB, extinction ratio: 35.0 dB).