Tunable and microwave dielectric properties of Ba0.5Sr0.5TiO3-BaWO4 composite ceramics doped with Co2O3

Co₂O₃ doped BaWO₄-Ba_0.5Sr_0.5TiO₃ composite ceramics, prepared by solid-state route, were characterized systematically, in terms of their phase compositions, microstructure and microwave dielectric properties. Doping of Co₂O₃ promoted grain growth, reduced Curie temperature and broadened phase-transition temperature range of BaWO₄-Ba_0.5Sr_0.5TiO₃, which were attributed mainly to the substitution of Co³⁺ for Ti⁴⁺ at B site in the perovskite lattice. Dielectric diffusion behaviors of the composite ceramics were discussed. The composite ceramics all had dielectric tunability of higher than 10% at 30 kV/cm and 10 kHz, with promising microwave dielectric properties. Specifically, the sample doped with 0.2 wt.% Co₂O₃ exhibited a tunability of 20%, permittivity of 225 and Q of 292 (at 1.986 GHz), making it a suitable candidate for applications in electrically tunable microwave devices.     

Effect of liquid-forming additives on the sintering and mechanical properties of Al2O3/3Y-TZP (30 vol.%) composite

Al₂O₃/3Y-TZP (30 vol.%) composite was pressurelessly sintered with addition of TiO₂MnO₂ and/or CaOAl₂O₃SiO₂ glass. It was found that TiO₂MnO₂ addition greatly enhanced the densification of the composite by the formation of a low-viscosity liquid at sintering temperature. In contrast, the high-viscosity liquid formed by CaOAl₂O₃SiO₂ glass improved mechanical properties because of its repressing effect on grain growth. The composite could be obtained at a temperature as low as 1400°C by co-doping with TiO₂MnO₂ and CAS glass. Bending strength of 552±64 MPa and fracture toughness of 6.03±0.22 MPa m^1/2 were obtained with a doping level of 2 wt.% TiO₂MnO₂ and 2 wt.% CAS glass.     

Luminescence response and CL degradation of combustion synthesized spherical SiO2:Ce nanophosphor

This study was aimed to systematically investigate the luminescence response of SiO₂:Ce³⁺ nanophosphors with different excitation sources. The powders were synthesized by using an urea assisted combustion method. SiO₂:Ce_1m% samples were also annealed at 1000 °C for 1 h in a charcoal environment to reduce incidental Ce⁴⁺ to partial Ce³⁺ ions. High resolution transmission electron microscopy (HRTEM) images of the as synthesized and annealed powder samples confirmed that the particles were spherical and in the size range of 3-8 nm in diameter. X-ray diffraction (XRD) and electron dispersion spectroscopy (EDS) results showed that the SiO₂ was crystalline and pure. Diffused reflectance, photoluminescence (PL) and cathodoluminescence (CL) results of the SiO₂:Ce³⁺ samples were obtained and compared with each other. The CL degradation and the surface reactions on the surface of the SiO₂:Ce³⁺ were studied with X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). A clear improvement in the chemical stability of the SiO₂:Ce³⁺ annealed at 1000 °C were obtained.     

Low temperature synthesis of SrS:Ce phosphor by carbothermal reduction method: Influence of sulfur and charge compensator on the luminescent properties

We report here on an ecologically friendly carbothermal reduction method to realize SrS:Ce phosphor. The method effectively reduces the preparation temperature by 100 °C. The effect of sulfur and charge compensator were studied separately and in combination, on the luminescent properties of SrS:Ce phosphor prepared from SrSO₄:Ce(SO₄)₂·4H₂O using this method without inert gas or hazardous gas (H₂S) environment. To analyze the role of charge compensator on the luminescent emission property of SrS:Ce, various fluxes, viz., NH₄Cl, NaCl were used. The synthesized products were characterized by XRD, photoluminescence emission and excitation spectroscopy (PLE). SrS:Ce showed a bright blue-green emission at 480 and 540 nm corresponding to energy bands originating from ²T_2g (5d) to ²F_7/2, ²F_5/2 (4f) of Ce³⁺ transitions. The characterization results showed the formation of SrS calcined at 900 °C for 5 h with an increase in blue-green luminescence intensity after the addition of sulfur and charge compensator, separately. When the sulfur and NH₄Cl were jointly added, the intensity of blue emission was enhanced, whereas, that of green emission was suppressed. The excitation spectrum showed a fundamental absorption of SrS host crystal lattice at 283 nm and Ce³⁺ absorption at 430 nm respectively. The CIE (Commission International de’Eclairge) chromaticity coordinates of the phosphor are also reported.     

The synthesis and optical property of solid-state-prepared YAG:Ce phosphor by a spray-drying method

Ce³⁺-activated yttrium aluminum garnet (Y₃Al₅O₁₂:Ce, YAG:Ce) powder as luminescent phosphor was synthesized by the solid-state reaction method. The phase identification, microstructure and photoluminescent properties of the products were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), absorption spectrum and photoluminescence (PL) analysis. Spherical phosphor particle is considered better than irregular-shaped particle to improve PL property and application, so this phosphor was granulated into a sphere-like shape by a spray-drying device. After calcinating at 1500 °C for 0, 4, and 8 h, the product was identified as YAG and CeO₂ phases. The CeO₂ phase content is decreased by increasing the calcination time or decreasing the Ce³⁺ doping content. The product showed higher emission intensity resulted from more Ce³⁺ content and larger grain size. The product with CeO₂ was found to have lower emission intensity. This paper presents the crystal structures of Rietveld refinement results of powder XRD data.     

TiO2-coated foams as a medium for solar catalysis

Sunlight irradiating the surface of the Earth represents a maximum input available for a solar catalytic process of 50 W_UV m⁻². We propose using high-porosity, metallic, reticulated foams as the support medium for the photocatalyst in order to improve the apparent quantum yield. The layer of TiO₂ was applied by dip-coating. The measurement of the degradation kinetics was carried out on a model target molecule, 2,4 dichlorophenol, at an initial concentration of 10 mg l⁻¹. The aim was to assess the efficiency of the foams as a photocatalytic media compared to that of a suspension of catalytic powder (Degussa P25) and the flat 2D support (Ahlstrom cellulose media). The apparent quantum yield of the foam scaffold carrying the TiO₂ was high, showing that, as with the powder suspension, foam makes good use of the UV rays to break down molecules. It is noteworthy that the apparent quantum yield of the foam tended towards that observed for suspensions which form the ideal support thanks to their optimal ability to harness the light.     

Photoemission study of the tin doped cerium oxide thin films prepared by RF magnetron sputtering

Ce-Sn-O mixed oxide films prepared by simultaneous Sn metal and cerium oxide magnetron sputtering were studied by high resolution photoemission. The analysis showed that the degree of reduction of the cerium oxide depends on the tin concentration in the film. Ce⁴⁺ → Ce³⁺ conversion is explained by a charge transfer from Sn atoms to unoccupied orbital Ce 4f⁰ of cerium oxide by forming Ce 4f¹ state. The X-ray Photoelectron Spectroscopy data were compared with study of the single-crystalline CeO₂ thin films and Sn/CeO₂(111) model system prepared and studied in situ excluding air exposure effects.     

Near-ultraviolet excitable Ca4Y6(SiO4)6O: Ce,Tb white phosphors for light-emitting diodes

The present investigation aims to demonstrate the potentiality of Tb³⁺ and Ce³⁺ co-doped Ca₄Y₆(SiO₄)₆O phosphors. By incorporation of Ce³⁺ into Ca₄Y₆(SiO₄)₆O: Tb³⁺, the excitation band was extended from short-ultraviolet to near-ultraviolet region. The energy transfer from Ce³⁺ to Tb³⁺ in Ca₄Y₆(SiO₄)₆O host was investigated and demonstrated to be a resonant type via a dipole–dipole mechanism with the critical distance of 10.2 Å. When excited by 352 nm, Ca₄Y₆(SiO₄)₆O: Ce³⁺, Tb³⁺ exhibited a brighter and broader violet-blue emission (421 nm) from the Ce³⁺ and an intense green emission (542 nm) from the Tb³⁺. Combining the two emissions whose intensities were adjusted by changing the doping levels of the co-activator, an optimized white light with chromaticity coordinates of (0.278, 0.353) is generated in Ca₄Y₆(SiO₄)₆O: 2% Ce³⁺, 8% Tb³⁺, and this phosphor could be potentially used in near-ultraviolet light-emitting diodes.     

Synthesis and characterization of photoluminescent cerium-doped yttrium aluminum garnet

Powder phosphor yttrium aluminum garnet (YAG), doped with trivalent cerium (Ce³⁺) is synthesized by sol-gel method. The formation of YAG and YAG:Ce (cerium-doped yttrium aluminum garnet) was investigated by means of X-ray diffraction (XRD). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were also used. The purified crystalline phases of YAG and YAG:Ce were obtained at 1000 °C. The maximum average grain size is about 20-23 nm for undoped samples and 28-34 nm for doped samples. The crystalline YAG:Ce emission shows one peak in the range 480-535 nm with the maximum near 520 nm. Photoluminescence (PL) intensity of 5d → 4f transition of Ce³⁺ increased with increasing annealing temperature. With increasing the concentration of Ce³⁺, the photoluminescence peak shifts towards the red region.     

Preparation of TiO2/Al-MCM-41 mesoporous materials from coal-series kaolin and photodegradation of methyl orange

TiO₂/Al-MCM-41 mesoporous materials were prepared via sol-gel method by loading titania onto Al-MCM-41 mesoporous molecular sieve by hydrothermal treatment from coal-series kaolin as raw material. The TiO₂/Al-MCM-41 mesoporous materials were characterized by XRD, FT-IR, HRTEM, N₂ adsorption-desorption and the photocatalytic degradation of methyl orange solution under visible light irradiation. The results showed that the TiO₂/Al-MCM-41 mesoporous materials possessed a high surface area of 369.9–751.3 m²/g and a homogeneous pore diameters of 2.3–2.8 nm. The titania crystalline phase was anatase, and the particles size of TiO₂ increased with TiO₂ content. The Al-MCM-41 mesoporous materials exhibited excellent photodegradation activity under visible-light irradiation for methyl orange.     

Novel composite interconnecting ceramics La0.7Ca0.3CrO3−δ/Ce0.8Sm0.2O1.9 for solid oxide fuel cells

In this paper, an interconnecting ceramic for solid oxide fuel cells was developed, based on the modification from La_0.7Ca_0.3CrO_3−δ by addition of Ce_0.8Sm_0.2O_1.9. It is found that addition of small amount Ce_0.8Sm_0.2O_1.9 into La_0.7Ca_0.3CrO_3−δ dramatically increased the electrical conductivity. For the best system, La_0.7Ca_0.3CrO_3−δ + 5 wt.% Ce_0.8Sm_0.2O_1.9, the electrical conductivity reached 687.8 S cm⁻¹ at 800 °C in air. In H₂ at 800 °C, the specimen with 3 wt.% Ce_0.8Sm_0.2O_1.9 had the maximal electrical conductivity of 7.1 S cm⁻¹. With the increase of Ce_0.8Sm_0.2O_1.9 content the relative density increased, reaching 98.7% when the Ce_0.8Sm_0.2O_1.9 content was 10 wt.%. The average coefficient of thermal expansion at 30-1000 °C in air increased with Ce_0.8Sm_0.2O_1.9 content, ranging from 11.12 × 10⁻⁶ to 12.46 × 10⁻⁶ K⁻¹. The oxygen permeation measurement illustrated a negligible oxygen ionic conduction, indicating it is still an electronically conducting ceramic. Therefore, this material system will be a very promising interconnect for solid oxide fuel cells.     

Design of Cu–Ce co-doped TiO<Subscript>2</Subscript> for improved photocatalysis

The fast recombination of photo-generated conduction band electrons (e _cb ^? ) and valance band holes (h _vb ⁺ ) of TiO₂ results in an unsatisfactory photocatalytic performance for organic degradation. To increase the efficiency of charge separation, TiO₂ was modified by Cu–Ce co-doping considering the better redox properties of copper–ceria oxide with respect to the single oxide, i.e., an easier electron capturing ability. An optimal Cu–Ce co-doped TiO₂ with the initial molar ratio of Cu/Ce at 3:1 was prepared by a hydrothermal method with the aim to greatly promote the charge separation, and characterized by XRD, BET, DRS, PL, HR-TEM, and XPS techniques. Upon ultraviolet light irradiation, it exhibits significantly enhanced photocatalytic activity, about 5.8 times that of Ti–HF. The presence of Cu²⁺ and Ce³⁺/Ce⁴⁺ benefits electrons captured by molecular oxygen, while an increased hydroxyl groups upon Cu–Ce co-doping consume more holes, resulting in prolonged lifetime of photo-generated carriers. Moreover, it is proved that electron transfers preferably from conduction band (CB) of TiO₂ to CB of CuO and then to nearby CeO₂.     

Preparation and super-hydrophilic properties of TiO2/SnO2 composite thin films

SnO₂-TiO₂ composite thin films were fabricated on soda-lime glass with sol-gel technology. By measuring the contact angle of the film surface and the degradation of methyl orange, we studied the influence of SnO₂ doping concentration, heat-treatment temperature and film thickness on the super-hydrophilicity and photocatalytic activity of the composite films. The results indicate that the doping of SnO₂ into TiO₂ can improve their hydrophilicity and photocatalytic activity, and the composite film with 1-5 mol% SnO₂ and heat-treated at 450°C is of super-hydrophilicity. The optimal SnO₂ concentration for the photocatalytic activity is 10 mol% and larger film thickness is helpful to reduce the contact angle of the composite films.     

Aluminium doped ceria–zirconia supported palladium-alumina catalyst with high oxygen storage capacity and CO oxidation activity

The Ce_0.5Zr_0.3Al_0.2O_1.9/Pd-γ-Al₂O₃ catalyst prepared by a mechanochemical route and calcined at 1000 °C for 20 h in air atmosphere to evaluate the thermal stability. The prepared Ce_0.5Zr_0.3Al_0.2O_1.9/Pd-γ-Al₂O₃ catalyst was characterized for the oxygen storage capacity (OSC) and CO oxidation activity in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique were employed. The OSC values of all samples were measured at 600 °C using thermogravimetric-differential thermal analysis. Ce_0.5Zr_0.3Al_0.2O_1.9/Pd-γ-Al₂O₃ catalyst calcined at 1000 °C for 20 h with a BET surface area of 41 m² g⁻¹ exhibited the considerably high OSC of 583 μmol-O g⁻¹ and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO₂/Pd-γ-Al₂O₃ and Ce_0.5Zr_0.5O₂/Pd-γ-Al₂O₃ for comparison.     

Physicochemical properties of solid-solid interactions in nanosized NiO-substituted Fe2O3/TiO2 system at 1200 °C

The solid-solid interactions between nanosized pure and NiO-substituted ferric and titanium(IV) oxides have been investigated using XRD technique and microstructure studies, also magnetic properties were studied using vibrating samples magnetometer (VSM). The amounts of substituting Ni²⁺ were x = 0, 0.2, 0.4, 0.6, 0.8 and 1 mole. A mixture equimolar proportions of finely powdered Fe₂O₃ and TiO₂ were mixed with NiO, ball milled, compressed at 250 kg/cm² and fired at 1200 °C for 4 h.The obtained results showed that with substituting Ni²⁺ concentration x = 0 only Fe₂TiO₅ phase is present (∼80 nm) which showed a very small saturation magnetic flux density (B_s), remnant magnetic flux density (B_r) and the maximum energy product (BH)_max. By the addition of x = 0.2 NiO, new phases were observed NiTiO₃ and NiFe₂O₄ of crystallite sizes 160 and 110 nm, respectively. By the increase of substituting Ni²⁺ concentration the NiTiO₃ and NiFe₂O₄ phases increased on the expense of Fe₂TiO₅ up to x = 0.4, then the increase in substituting Ni²⁺ concentration led to a decrease in Fe₂TiO₅ and NiTiO₃ while NiFe₂O₄ increases which results in a great improvement of magnetic properties.All samples exhibit a catalytic activity towards H₂O₂ decomposition and the values of rate constant increase with increasing amount of Ni²⁺ substituting. The most acidic active sites are shown by specimens substituted with x = 0 this concludes that H₂O₂ decomposition is not favored on acidic active sites.     

Performance of Ni/ScSZ cermet anode modified by coating with Gd0.2Ce0.8O2 for a SOFC

A Ni/scandia-stabilized zirconia (ScSZ) cermet anode was modified by coating with nano-sized gadolinium-doped ceria (GDC, Gd_0.2Ce_0.8O₂) within the pores of the anode for a solid oxide fuel cell (SOFC). X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed in the anode characterizations. Open circuit voltages (OCVs) increased from 1.027 to 1.078 V, and the maximum power densities increased from 238 to 825 mW/cm², as the operating temperature of a SOFC with 2.0 wt.%GDC-coated Ni/ScSZ anode was increased from 700 to 850 °C in humidified hydrogen. The coating of nano-sized Gd_0.2Ce_0.8O₂ particle within the pores of the porous Ni/ScSZ anode significantly improved the performance of anode supported cell. Electrochemical impedance spectra (EIS) illustrated that the cell with Ni/ScSZ anode exhibited far greater impedances than the cell with 2.0 wt.%GDC-coated Ni/ScSZ anode. Consequently, 2.0 wt.%GDC-coated Ni/ScSZ anode could be used as a novel anode material for a SOFC due to better electrochemical performance.     

Properties and performance of La1.6Sr0.4NiO4+δ-Ce0.8Sm0.2O1.9 composite cathodes for intermediate temperature solid oxide fuel cells

La_1.6Sr_0.4NiO_4+δ-Ce_0.8Sm_0.2O_1.9 composite cathodes were prepared successfully using combustion synthesis method for intermediate temperature solid oxide fuel cells. The chemical compatibility, thermal expansion behavior, electrical conductivity and electrode performance were studied. The X-ray diffraction of La_1.6Sr_0.4NiO_4+δ-Ce_0.8Sm_0.2O_1.9 composite result proved a slight reaction between La_1.6Sr_0.4NiO_4+δ and Ce_0.8Sm_0.2O_1.9. Both the thermal expansion coefficient and the electrical conductivity of La_1.6Sr_0.4NiO_4+δ-Ce_0.8Sm_0.2O_1.9 decreased with increasing Ce_0.8Sm_0.2O_1.9 content. AC impedance spectroscopy measurements indicated that the addition of 30 wt% Ce_0.8Sm_0.2O_1.9 to La_1.6Sr_0.4NiO_4+δ exhibited the lowest polarization resistance (0.238 Ωcm²) at 800 °C in air, which was only one fourth of the La_1.6Sr_0.4NiO_4+δ electrode measured at the same temperature.     

Decomposition of the molecular precursor Bu4Sn6S6 on the surface of TiO2 to prepare semiconductor composite photocatalysts

In this work, the single source organometallic precursor Bu₄Sn₆S₆ was impregnated and decomposed on the surface of TiO₂ to produce semiconductor composites. ¹¹⁹Sn Mössbauer, Raman and ultra violet/visible spectroscopies, powder X-ray diffraction, temperature programmed reduction and surface area suggest for Sn contents of 1, 5 and 10 wt%, the formation of a highly dispersed unstable SnS phase which is readily oxidized by air at room temperature to form SnO₂ on the TiO₂ surface. The composite with Sn 30 wt% produced a mixture with the phases SnS/γ-Sn₂S₃ and SnO₂. Photocatalytic experiments with the composites SnX_n/TiO₂ using the textile dye Drimaren red as a probe molecule showed a first-order reaction with rate constants k_absorbance for the composites with Sn 1 and 5% higher than pure TiO₂ which was explained by the formation of the more active photocatalyst composite SnO₂/TiO₂.     

High-temperature anomalies of dielectric constant in TiO2 thin films

Anatase and rutile TiO₂ thin films were prepared by chemical vapor deposition with precursors Ti(OPrⁱ)₄ and Ti(dpm)₂(OPrⁱ)₂ (dpm = 2,2,6,6-tetramethylheptane-3,5-dione and Prⁱ = isopropyl), respectively. The dielectric properties of TiO₂ thin films have been studied in 20-1100 K temperature range in air, in controlled Ar/O₂ atmospheres, and in vacuum with silicon-based metal-insulator-semiconductor Au/TiO₂/Si capacitors. High-temperature (T_c ∼ 980 K) anomalous behavior of dielectric constant was observed in both anatase and rutile TiO₂ thin films.     

Synthesis and structural characterization of Ce-doped bismuth titanate

Ce-modified bismuth titanate nanopowders Bi_4−xCe_xTi₃O₁₂ (x ≤ 1) have been synthesized using a coprecipitation method. DTA/TG, FTIR, XRD, SEM/EDS and BET methods were used in order to investigate the effect of Ce-substitution on the structure, morphology and sinterability of the obtained powders. The phase structure investigation revealed that after calcinations at 600 °C powder without Ce addition exhibited pure bismuth titanate phase; however, powders with Ce (x = 0.25, 0.5 and 0.75) had bismuth titanate pyrochlore phase as the second phase. The strongest effect of Ce addition on the structure was noted for the powder with the highest amount of Ce (x = 1) having a cubic pyrochlore structure. The presence of pure pyrochlore phase was explained by its stabilization due to the incorporation of cerium ions in titanate structure. Ce-modified bismuth titanate ceramic had a density over 95% of theoretical density and the fracture in transgranular manner most probably due to preferable distribution of Ce in boundary region.