Fabrication and properties of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> composites

Composites in the form of precipitated powders, hybrid xerogels, and SiO₂ core/TiO₂ shell particles have been produced via hydrolysis of precursors (alkoxides and inorganic derivatives of titanium and silicon) and have been characterized by differential thermal analysis, X-ray diffraction, adsorption measurements, and macroelectrophoresis. The results demonstrate that heat treatment of the composites leads to crystallization of the titanium-containing component and, accordingly, reduces their specific surface area. Hydrothermal treatment enables the fabrication of materials in which TiO₂ nanocrystals are evenly distributed over an amorphous SiO₂ matrix.     

Low-temperature sintering of SiC reticulated porous ceramics with MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> additives as sintering aids

SiC reticulated porous ceramics (SiC RPCs) was fabricated with polymer replicas method by using MgO–Al₂O₃–SiO₂ additives as sintering aids at 1,000∼1,450 °C. The MgO–Al₂O₃–SiO₂ additives were from alumina, kaolin and Talc powders. By employing various experimental techniques, zeta potential, viscosity and rheological measurements, the dispersion of mixed powders (SiC, Al₂O₃, talc and kaolin) in aqueous media using silica sol as a binder was studied. The pH value of the optimum dispersion was found to be around pH 10 for the mixtures. The optimum condition of the slurry suitable for impregnating the polymeric sponge was obtained. At the same time, the influence of the sintering temperature and holding time on the properties of SiC RPCs was investigated. According to the properties of SiC RPCs, the optimal sintering temperature was chosen at 1,300 °C, which was lower than that with Al₂O₃–SiO₂ additives as sintering aids.     

Preparation and electrical properties of semiconducting strontium—lead titanate PTCR ceramics

A typical positive temperature coefficient of resistance (PTCR) effect in yttrium-doped (Sr, Pb)TiO₃ ceramics made by chemical processing was obtained for the first time. The results show that the room temperature resistivity is lower than 10² Ω cm and the resistivity jump is above 10⁶. The breakdown voltage is above 340 V mm⁻¹ (a.c.). The sintering temperature is about 1100°C, lower than for conventional BaTiO₃ ceramics. This revised version was published online in July 2006 with corrections to the Cover Date.     

SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> fibers from titanium-modified polycarbosilane

We developed a process for preparing SiO₂/TiO₂ fibers by means of precursor transformation method. After mixing PCS and titanium alkoxide, continuous SiO₂/TiO₂ fibers were fabricated by the thermal decomposition of titanium-modified PCS (PTC) precursor. The tensile strength and diameter of SiO₂/TiO₂ fibers are 2.0 GPa, 13 μm, respectively. Based on X-ray diffraction (XRD), scanning electron microscopy (SEM), and high resolution transmission electron microscopy (HRTEM) measurements, the microstructure of the SiO₂/TiO₂ fibers is described as anatase–TiO₂ nanocrystallites with the mean size of ~10 nm embedded in an amorphous silica continuous phase.     

Fabrication of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> double layer thin films with self-cleaning and photocatalytic properties

Transparent antireflective SiO₂/TiO₂ double layer thin films were prepared using a sol–gel method and deposited on glass substrate by spin coating technique. Thin films were characterized using XRD, FE-SEM, AFM, UV–Vis spectroscopy and water contact angle measurements. XRD analysis reveals that the existence of pure anatase phase TiO₂ crystallites in the thin films. FE-SEM analysis confirms the homogeneous dispersion of TiO₂ on SiO₂ layer. Water contact angle on the thin films was measured by a contact angle analyzer under UV light irradiation. The photocatalytic performance of the TiO₂ and SiO₂/TiO₂ thin films was studied by the degradation of methylene blue under UV irradiation. The effect of an intermediate SiO₂ layer on the photocatalytic performance of TiO₂ thin films was examined. SiO₂/TiO₂ double layer thin films showed enhanced photocatalytic activity towards methylene blue dye.     

Ultra-long SiO<Subscript>2</Subscript> and SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> tubes embedded with Pt nanoparticles using magnus green salt as templating structures

For the first time, magnus green salt (MGS, [Pt(NH₃)₄][PtCl₄]) fibers precipitated by solvent modification have been employed as a structure-directing modifier to synthesize single silica and silica/titania microtubes via a sol–gel process. In the case of titania tubes, tetraethylorthosilicate must be used as a capping agent to hinder the aggregation of primary MGS fibers and to serve as a protective layer against thermal stress during the metal salt fiber reduction. This implies that SiO₂/TiO₂ tubes result. The synthesized tubular materials were imaged by scanning and transmission electron microscopy, while their composition was determined by energy dispersive X-ray analysis and thermogravimetric analysis. Crystallinity and thermal stability of the tube walls were studied using X-ray diffraction analysis. The obtained oxide tubes possess high aspect ratios (80–200) because they are up to 60 μm in length, but only 300–700 nm in thickness. The key aspects of the synthesis approach are that the templating MGS fibers control the internal diameter of the oxide tubes, while the synthesis conditions control their wall thickness. The suggested method is a simple approach which produces, at low temperatures, very long oxide tubes with a very high amount of Pt (48–51 wt%) directly incorporated inside the tubes. To the best of our knowledge, filling of SiO₂ or SiO₂/TiO₂ nanotubes with such a dense population of Pt metal nanoparticles has not been demonstrated so far; our own experiments with [Pt(NH₃)₄](HCO₃)₂ as templating salt formed only tubes containing about 40 wt% Pt and were only about 20 μm long. The now formed more Pt-rich tubes are expected to have vivid applications in (photo)catalysis and in fabricating novel devices, such as nano- or sub-microcables.     

Dielectric properties of Yb<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped barium strontium calcium titanate thick films for microwave device applications

(Ba_0.56Sr_0.34Ca_0.10)TiO₃ (BSCT) thick films doped with 0.1 mol% MnCO₃ and Yb₂O₃ (0.1–0.7 mol%) were fabricated by the screen-printing method on the alumina substrate. The structural and electrical properties as a function of Yb₂O₃ amount were investigated. All BSCT thick films showed the formation of a complete solid solution in a cubic perovskite polycrystalline structure. Average grain size of the specimen doped with 0.7 mol% Yb₂O₃ was about 2.7 μm. The thickness of all BSCT thick films was approximately 50–55 μm. The relative dielectric constant, dielectric loss, and tunability of the BSCT thick films doped with 0.3 mol% Yb₂O₃ were 2,966, 0.7, and 14.3%, respectively.     

Frequency and temperature dependence of electrical properties of barium and gadolinium substituted SrBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

Barium strontium gadolinium bismuth niobate (Ba_0.1Sr_0.81Gd_0.06Bi₂Nb₂O₉, BSGBN) ceramics were prepared by using the conventional solid-state reaction method. The dielectric permittivity, modulus and impedance spectroscopy studies on BSGBN were investigated in the frequency range, 45 Hz–5 MHz and in the temperature range from room temperature (RT) to 570 °C. The dielectric anomaly with a broad peak was observed at 470 °C. Simultaneous substitution of Ba²⁺ and Gd³⁺ increases the transition temperature of SrBi₂Nb₂O₉ (SBN) from 392 to 470 °C. XRD studies in BSGBN revealed an orthorhombic structure with lattice parameters a = 5.4959 Å, b/a = 1.000, c = 25.0954 Å. Impedance and modulus plots were used as tools to analyse the sample behaviour as a function of frequency. Cole-Cole plots showed a non-Debye relaxation. Also, dc and ac conductivity measurements were performed on BSGBN. The electric impedance which describes the dielectric relaxation behaviour is fitted to the Kohlrausch exponential function. Near the phase transition temperature, a stretched exponential parameter β indicating the degree of distribution of the relaxation time has a small value.     

Dielectric properties and electrical conductivity of ZrO<Subscript>2</Subscript>-CeO<Subscript>2</Subscript> ceramics

ZrO₂-CeO₂ (10, 18, and 23 mol % CeO₂) solid solutions have been synthesized via coprecipitation. The powders have been sintered at 1875 K, and the electrical conductivity and dielectric properties of the resultant ceramics have been studied. The dielectric relaxation observed in the ceramics can be understood in terms of ionic transport accompanied by the formation of dipoles relaxing in an ac electric field.     

Bio-inspired design of a transparent TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite gel coating with adjustable wettability

Although the superhydrophobicity and transparence are generally two contradictory characters as the roughness factor, it is literature abundant for achieving both of these two purposes. To our knowledge, the integration multipurpose (transparent, superhydrophobic, superhydrophilic, underwater superoleophobicity, anti-fogging, and photo-controllable ability) in one has not been reported so far and these are vital for their promising applications in various aspects which can attract broad attention from scholars to engineers. In this work, we are successful to bio-inspired design of a kind versatile transparent nanocoating with superhydrophobic or superhydrophilic/underwater superoleophobic properties. The TiO₂/SiO₂ nanocoatings can be transformed from superhydrophobicity into superhydrophilicity and underwater superoleophobicity after heat treatment (450 °C and 2 h). If it was coated on conductive glass, the electrical conductivity was impervious, while the wettability can be manipulated. Importantly, both these superhydrophobic and superhydrophilic TiO₂/SiO₂ composite nanocoatings were endowed with photo-induced self-cleaning nature and these antifouling coatings could prolong their service life.     

Structure and microwave dielectric properties of ZnTa<Subscript>2</Subscript>O<Subscript>6</Subscript> ceramics with TiO<Subscript>2</Subscript> and ZrO<Subscript>2</Subscript> additions

Ceramic samples based on ZnTa2O₆ and ZnTa₂O₆–MO₂ (M = Ti, Zr) systems have been obtained by the solid state ceramic route. The phase composition and microstructure of samples were investigated. The effect of the aliovalent substitution of ions Zn²⁺ and Ta⁵⁺ by M⁴⁺ (M = Ti, Zr) in the structure of ZnTa₂O₆ on microwave dielectric properties of ceramics was studied. The way of the compensation of the positive temperature coefficient of resonant frequency of dielectric resonators based on ZnTa₂O₆ ceramics with using the aliovalent substitution of cations was proposed. Dielectric resonators with the high temperature stability of the resonant frequency and high dielectric properties in the microwave range based on the ZnTa₂O₆–ZrO₂ system were obtained for application in electronics.     

Effect of additives on the pore structure of ceramics based on crystalline SiO<Subscript>2</Subscript>

We have studied a method of controlling the pore structure of ceramics based on crystalline silica by introducing different burnable additives into the starting mixture. We have developed mathematical models in the form of best fit equations, which adequately represent the relationships between the burnable additive content of the starting mixture, the porosity of the ceramic samples, and their mechanical strength.     

Low-temperature sintering and microwave dielectric properties of TiO<Subscript>2</Subscript>-based LTCC materials

Temperature stable high-K LTCC material was prepared. The influence of fabrication process on the crystalline phases, microstructures and microwave dielectric properties of TiO₂-Bi₂O₃-CuO ceramics were investigated. The crystalline phases and microstructures of TiO₂-Bi₂O₃-CuO ceramics were investigated by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. It was found that rutile TiO₂ phase and Bi₂Ti₄O₁₁ phase co-existed in the TiO₂-Bi₂O₃-CuO ceramics. Separate TiO₂ grains and Bi₂Ti₄O₁₁ grains distributed uniformly in the ceramic matrix. The composition 0.92TiO₂-0.08Bi₂Ti₄O₁₁ with 2 wt% CuO addition that was sintered at 900 °C for 2 h showed high dielectric constant (ε_r ~ 81), high quality factor (Q × f ~ 3,500 GHz) and near zero temperature coefficient of resonant frequency (τ_f ~ −5.1 ppm/°C), meanwhile the compatibility test showed that it could co-fire with silver electrode. The processing-microstructure-property interrelationship was also studied.     

Effect of Mn<Superscript>2+</Superscript> doping on the temperature coefficient of capacitance of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript>-doped BaTiO<Subscript>3</Subscript> ceramics

The effect of Mn²⁺ on the temperature coefficient of capacitance (TCC) of TiO₂/SiO₂-doped BaTiO₃ ceramics has been investigated. The experiment has shown that the high temperature peak of TCC exhibited a continuous enhancement when Mn²⁺ concentration increased and X8R specification was gradually met. The secondary phase Ba₂TiSi₂O₈ was found in all samples. SEM and XRD analyses have proved that Mn²⁺ could depress the crystallization of TiO₂/SiO₂ in BaTiO₃ ceramics. The microstrain study through MAUD analysis depicted that the high temperature peak of TCC was dependent on the microstrain of samples to a certain extent. The Mn²⁺ could be a useful dopant for ameliorating the TCC of TiO₂/SiO₂-doped BaTiO₃ ceramics. The text was submitted by the authors in English.     

Low temperature sintering and dielectric properties of Ba<Subscript>3</Subscript>(VO<Subscript>4</Subscript>)<Subscript>2</Subscript> microwave ceramics using Co<Subscript>2</Subscript>O<Subscript>3</Subscript> additives

The Ba₃(VO₄)₂–x wt% Co₂O₃ (x?=?0.5–5) ceramics were prepared by the solid state reaction method in order to reduce the sintering temperature. The effects of the Co₂O₃ additions on the phase composition, microstructures, sintering characteristics and microwave dielectric properties of Ba₃(VO₄)₂ ceramics are investigated by an X-ray diffractometer, a scanning electron microscope and a network analyzer. As a result, the Q?×?f value of 54,000 GH, the ε _r of 14.6 and the τ_f value of +58.5 ppm/°C were obtained in the sample of the Ba₃(VO₄)₂–3 wt% Co₂O₃ ceramic sintered at the temperature of 925 °C, which is capable to co-fire with electrode metal of high conductivity such as Ag (961 °C). Moreover, the Q?×?f values of the sample with Co₂O₃ higher than that of 3 wt% additions decreased because of the formation of Ba₂V₂O₇ phase.     

Electrical and optical properties of TiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript>:Fe thin films

TiO₂ and TiO₂:Fe thin films have been grown by electron beam evaporation and the influence of doping and heat treatment on their electrical and optical properties has been studied.     

Phase transition and electrical properties in the Li-modified Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-based lead-free ceramics

Phase transition and electrical properties were demonstrated for a Li-modified Bi_0.5Na_0.5TiO₃-based solid solution. (0.935 − x)Bi_0.5Na_0.5TiO₃ − xBi_0.5Li_0.5TiO₃ − 0.065BaTiO₃ with 0.5 mol% Mn doping was prepared by a conventional solid state reaction method. Close inspection of X-ray diffraction patterns indicated that no characteristic peaks splitting happened, indicating the pseudocubic structure for all the compositions. At a critical composition x of 0.06, optimized performance was obtained with piezoelectric constant d ₃₃ of 176 pC/N, electromechanical coupling factors k _P of 0.33, and k _t of 0.52, respectively. In addition, it was found that the Li substitution could lead to a disruption of long-range ferroelectric order and obtain enhanced frequency dispersion behavior accompanied with the decreasing of the depolarization temperature T _d, which was responsible for the observed weaker ferroelectric polarization and electromechanical response. The composition induced structure evolution was also discussed combined with the Raman spectroscopy.     

Sorption of U(VI) onto TiO<Subscript>2</Subscript>/ZrO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> Mesoporous Materials from Sulfate Solutions

New nanostructured mesoporous materials of the composition TiO₂/ZrO₂/SiO₂ were prepared by the template sol–gel method using a siloxane–acrylate emulsion as a template. The morphology and structure of these materials and their ability to take up U(VI) were studied. The influence of various factors (ZrO₂ content, pH of solution) on the sorption properties was studied. The suggested materials allow efficient sorption of U(VI) from sulfate solutions with low U(VI) concentrations and can be used in final purification processes.     

Ultrasound velocity and absorption in BeO,Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, ZrO<Subscript>2</Subscript>, and SiO<Subscript>2</Subscript> ceramics

We have measured the ultrasound velocity and absorption in BeO, Al₂O₃, ZrO₂, and SiO₂ ceramics. The results indicate that the ultrasound velocity in oxide ceramics depends on the nature of the basic oxide component, the density of the material, and the preferential alignment of the grains. The ultrasound velocity in ceramics is shown to correlate with their thermal conductivity: with increasing thermal conductivity, the ultrasound velocity increases. The ultrasound absorption in oxide ceramics decreases with decreasing temperature, and vice versa, with increasing temperature, the ultrasound attenuation coefficient increases.     

PTCR effect in BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript>-doped BaTiO<Subscript>3</Subscript> ceramics

The influences of BaBi₂Nb₂O₉ content on the electrical property and the microstructure of BaTiO₃-based materials have been studied. With an increase in BaBi₂Nb₂O₉ content the grain size decreases. All the prepared BaBi₂Nb₂O₉ doping BaTiO₃-based thermistors show typical PTC effect. As the amount of BaBi₂Nb₂O₉ added in BaTiO₃-based ceramics increases, resistivity appears to exhibit a minimum value. At high BaBi₂Nb₂O₉ content (≥0.0875), the resistivity increased again with increasing BaBi₂Nb₂O₉ content. At a given content of BaBi₂Nb₂O₉, the influence of sintering temperature on the electrical properties of samples has been investigated. A minimum of room temperature resistivity is obtained at the sintering temperature equal to 1,290 °C at a given content of BaBi₂Nb₂O₉.