Investigation on thermal and microstructural characterization of the TeO2-WO3 system

Thermal and microstructural characterization of the TeO₂-WO₃ binary system was accomplished by applying differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. Different compositions of the (1 − x)TeO₂-xWO₃ system, where x varies between 0.02 and 0.80 in molar ratio were studied. The samples were prepared by melting high purity powder mixtures of TeO₂ and WO₃ in a platinum crucible with a closed lid at 750 °C for 30 min and quenching in water bath. The glass forming range of the binary system was detected as 0.04 ≤ x ≤ 0.35 in molar ratio. As-cast samples were heat-treated above the crystallization peak temperatures at 550 °C for 24 h to obtain thermal stability and the phase stability of the binary system was investigated by performing systematical thermal, phase and microstructural characterizations with the heat-treated samples. The eutectic reaction of the binary system was detected at 617 ± 3 °C, the endothermic reaction indicating the phase transformation reaction of WO₃ from orthorhombic to tetragonal was determined at 743 ± 1 °C. α-TeO₂ and orthorhombic WO₃ crystalline phases were found to be present in the final structure when the total crystallization was achieved. Microstructural characterization of the TeO₂-WO₃ system was realized for a wide compositional range for the first time in the literature.     

Subsolidus phase relations in the ZnO-WO3-Bi2O3 system

The subsolidus phase relations of the ternary system ZnO-WO₃-Bi₂O₃ were investigated by means of X-ray diffraction (XRD). Six binary compounds and seven 3-phase regions were determined, and no ternary compounds were found in this ternary system. The phase diagram of pseudobinary system ZnO-Bi₂WO₆ was also constructed through XRD and differential thermal analysis (DTA) methods, which forms eutectic system with eutectic temperature about 945 °C, the corresponding eutectic component is 35 mol% ZnO and 65 mol% Bi₂WO₆.     

Preparation of nanosized sodium-aluminum tungstate, NaAl(WO4)2

Investigations are carried out for preparing nanosized pure phase of NaAl(WO₄)₂ by means of solid state synthesis with mechanical activation, applying the sol-gel method (Pechini) and by co-precipitation. It is shown that it is not possible to obtain pure phase when the initial substances are in stoichiometric amounts due to the simultaneous formation of a number of accompanying tungstate phases. The reasons for their origin are discussed. A method is demonstrated for obtaining a pure phase of NaAl(WO₄)₂ by co-precipitation of aqueous Na₂WO₄ and Al(NO₃)₃ solutions with considerable excess of Na₂WO₄. It is proved that NaAl(WO₄)₂ with particle size 40-80 nm is obtained with final synthesis of the powders at temperature 600-650 °C and duration of thermal treatment of 1-2 h.     

Synthesis and electrochemical properties of Li4Ti5O12

The spinel compound Li₄Ti₅O₁₂ was synthesized by a solid state method. In this synthesizing process, anatase TiO₂ and Li₂CO₃ were used as reactants. The influences of reaction temperature and calcination time on the properties of products were studied. When calcination temperature was 750 °C and calcination temperature was 24 h, the products exhibited good electrochemical properties. Its discharge capacity reached 160 mAh g⁻¹ and its capacity retention was 97% at the 50th cycle when the current rate was 1 C. When current rate increased to 10 C, its first discharge capacity could reach 136 mAh g⁻¹, and its capacity retention was 85% at the 50th cycle.     

Characterization of paramagnetic KHo(WO4)2 nanocrystals: Synthesized by polymeric mixed-metal precursor sol-gel method

Nanocrystalline KHo(WO₄)₂ (KHW) particles were successfully synthesized via conventional Pechini sol-gel method. Prepared precursor gel was calcined at 250, 550, 600, 650 and 700 °C, and the resulting samples were analyzed with TG-DTA, powder X-ray diffraction, FT-IR, Raman, FESEM, TEM, UV-Vis-NIR (diffuse reflectance spectrum (DRS)), fluorescence and vibrating sample magnetometer (VSM). Thermal degradation of derived gel was observed up to 400 °C and phase formation starts from 550 °C. The product phase formation at higher annealing temperature was investigated by means of powder XRD. Organic liberation in the samples with respect to temperature was analyzed using FT-IR spectrum. Raman spectrum reveals the formation of tungsten ribbons as well as the quality of the samples while increasing the calcination temperature. The nano size of the synthesized particles was confirmed with FESEM and TEM micrographs. Reflectance and emission studies reveal the corresponding absorption and emission properties of trivalent state holmium ion. Paramagnetic behavior of the derived KHW was confirmed with VSM results.     

Structural, optical and charge transport study of rutile TiO2 nanocrystals at two calcination temperatures

In this study the influence of two different calcination temperatures 80 °C and 450 °C on the structural, optical and charge transport properties of rutile TiO₂ nanocrystals has been investigated. TiO₂ nanocrystals have been prepared at low temperature by a simple hydrolysis method using titanium tetrachloride as starting precursor. The results of X-ray diffraction (XRD) showed that the prepared nanocrystals have a rutile tetragonal crystalline structure. Specific surface area of 80 °C and 450 °C calcinated rutile TiO₂ nanocrystals are 25.38 × 10⁵ cm²/g and 7.61 × 10⁵ cm²/g respectively, which has been calculated by X-ray diffraction data. Williamson-Hall plot results indicate the presence of compressive strain at 80 °C and tensile strain at 450 °C. Ultraviolet-visible (UV-vis) absorption spectroscopy is used to calculate the band gap of the material and the shift in absorption edge and it has been observed that the absorption spectra are strongly modified by the calcination temperature. The red-shift in photoluminescence (PL) is attributed to the change in strain from compressive to tensile. Photoconductivity (PC) measurements showed that capture cross-section of 80 °C (R1) and 450 °C (R2) calcinated rutile nanocrystals are 55.10 × 10⁻¹⁰ and 39.50 × 10⁻¹⁰ cm² respectively. High value of electron life-time, low value of radiative recombination and a four order increase in photogenerated charge carriers have been reported for the rutile TiO₂ nanocrystals calcinated at 450 °C.     

Preparation of WO3 network squares for ultrasensitive photodetectors

Three-dimensional WO₃ network squares have been fabricated on a large scale by a hydrothermal method at 160 °C without any template or surfactant. The characterization of the network squares with X-ray diffraction, scanning electron microscopy, and transmission electron microscopy indicates a single crystalline hexagonal structure with a square of side length up to 20 μm. The influence of pH value on the morphology of the final product has been studied, indicating that more uniform WO₃ network squares can be obtained at pH 1.7. A possible growth mechanism involves the Ostwald ripening, oriented attachment and etching effect. The UV-vis reflection spectrum indicates a band gap of ∼3.2 eV. The photodetector based on a single WO₃ network square shows remarkable photosensitivity under intermittent illumination of the simulated sunlight, which could mainly be attributed to the specific network structure of WO₃ and the Schottky contacts.     

Effect of vanadium on synthesis of WC nanopowders by thermal processing of V-doped tungsten precursor

The effect of vanadium on the synthesis of WC nanopowders by carbon thermal processing of V-doped tungsten precursor has been discussed. The V-doped tungsten precursor was prepared by a wet chemical method with ammonium tungstate and ammonium vanadate as its starting materials. The precursor was carbonized in the vacuum furnace using phenol formaldehyde resin as a carbon agent. The results of XRD revealed that the tungsten oxide and vanadium oxide obtained from the precursor preparation formed V–O–W bronze with the structure of WO₃ · 0.33H₂O. The carbonization reactions of WO₃ with 1 wt% of vanadium took place in a temperature range from 900 to 1050 °C to obtain V-doped WC nanopowder. The results of particle size measurement and morphological analysis show that the vanadium effectively inhibits the particle growth of tungsten carbide powder during carbonization processes, resulting in the particle size to be within the range from 64 to 184 nm after heat treatment in the temperature range from 900 to 1200 °C. V₂O₃ particles decomposed from V–O–W bronze can act as a nucleation aid for tungsten during reduction, and those on the surface of tungsten powder can hinter the growth of tungsten carbide crystal by the pinning effect.     

Inhibition of tungsten particle growth during reduction of V-doped WO3 nanoparticles prepared by co-precipitation method

The effect of vanadium on the tungsten particle growth during hydrogen reduction has been discussed. The nanostructured V-doped WO₃ powder was synthesized by co-precipitation method with ammonium tungstate and ammonium metavanadate as its starting materials and was then reduced in hydrogen atmosphere. The products were characterized by X-ray diffractometry, scanning electron microscopy, thermogravimetric analysis and small angle X-ray scattering. It was observed that the vanadium added to tungsten oxide formed tungsta-vanadate solid solution and was then reduced to V–O–W bronze, V_xWO_3−y, during the early stage of hydrogen reduction and decomposed continuously to α-W and V₂O₃ during the entire WO₂ → W transition. The results of particle size measurement and morphological analysis showed that the addition of vanadium could effectively inhibit the particle growth of tungsten powder during the reduction process. The addition of vanadium mainly effects on nucleation of tungsten at the lower temperatures below 850 °C because the slow decomposition of V–O–W bronze continuously provides the nucleation sites on the surface of WO₂ particles during reduction via impeding the formation of WO₂(OH)₂ and providing of nucleation aids for W deposition from the surrounding WO₂.     

The effect of calcining temperatures on the phase purity and electric properties of CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ (CCTO) ceramics are prepared by the traditional solid-state reaction method under the same sintering conditions. The effect of calcining temperatures for the powders before sintering on the microstructure and electric properties of CCTO ceramics has been investigated. The XRD patterns for the powder calcined at 950 °C show that some measure of second phases (CaTiO₃, TiO₂ and CuO) can be found except a considerable amount of CCTO phase in them and the content of second phases decrease markedly as the calcining temperature is raised to 1000 °C. The XRD patterns for the powder calcined at 1050 °C indicate that the powder has been basically formed into a single CCTO phase except a small quantity of CaTiO₃ phase, which is attributed to CuO volatilizing in the calcining process. Furthermore, the XRD patterns for the CCTO pellets sintered at 1080 °C/10 h manifest that all the second phases have disappeared after the sintering process except that a very weak peak of CaTiO₃ can still be seen in the XRD pattern for the pellets made of the powder calcined at 1050 °C. The electric properties measurement demonstrates that the lower calcining temperature for the raw powder is helpful to increase the values of permittivity and the higher calcining temperature is helpful to improve the non-ohmic properties. The non-ohmic characteristic has a behavior reverse to that of the permittivity, which can be ascribed to the change in the height of Schottky barriers.     

Structure and mechanical properties of TiAlSiN/Si3N4 multilayer coatings

TiAlSiN/Si₃N₄ multilayer coatings which have different separate layer thicknesses of TiAlSiN or Si₃N₄ were deposited onto glass sheets, single-crystal silicon wafers and polished WC-Co substrates by reactive magnetron co-sputtering. The morphology, crystalline structure and thickness of the as-prepared multilayer coatings were characterized by TEM, SEM, XRD and film thickness measuring instrument. The mechanical properties of the coatings were evaluated by a nanoindenter. The effects of monolayer thickness on the microstructure and properties of TiAlSiN/Si₃N₄ multilayer coatings were explored. The coatings showed the highest hardness when the thickness of Si₃N₄ and TiAlSiN monolayers was 0.33 nm and 5.8 nm, respectively. The oxidation characteristics of the coatings were studied at temperatures ranging from 700 °C to 900 °C for oxidation time up to 20 h in air. It was found that the coatings displayed good oxidation resistance.     

Microwave properties of Ba(Zn1/3Ta2/3)O3 dielectric resonators

Ba(Zn_1/3Ta_2/3)O₃ (BZT) dielectric resonators were prepared by solid-state reaction. The starting materials were BaCO₃, ZnO, and Ta₂O₅ powders with high purity. The double calcined BZT pellets were sintered in air at temperatures of 1575, 1600, 1625, and 1650 °C for 4 h. The X-ray diffraction data allowed the study of the unit cell distortion degree and the presence of the secondary phases. A long-range order with a 2:1 ratio of Ta and Zn cations on the octahedral positions of the perovskite structure was observed with the increase of the sintering temperature. The dielectric constant of BZT resonators measured around 6 GHz was between 26 and 28. High values of Q × f product (120 THz) were obtained for BZT resonators sintered at 1650 °C/4 h. The temperature coefficient of the resonance frequency exhibits positive values less than 6 ppm/°C. The achieved dielectric parameters recommend BZT dielectric resonators for microwave and millimeter wave applications.     

Formation of zinc aluminum mixed metal oxide nanostructures

We report a method for synthesizing zinc aluminum layered double hydroxide (ZnAl:LDH) nanostructures at room temperature. The ZnAl:LDH nanoplates could be converted into zinc aluminum mixed metal oxide (MMO) nanostructures by calcination in air. The crystalline nature and morphology of the MMO nanostructures could be tuned by varying the calcination temperature. At low calcination temperatures (450-650 °C), nanostructures were composed of crystalline ZnO regions and amorphous regions. The crystalline orientations of the ZnO crystal grains were almost identical throughout the nanostructure. At calcination temperatures above 750 °C, ZnAl₂O₄ crystal grains appeared and amorphous regions could not be found in MMO nanostructures. As the calcination temperature increased, the crystal grain size and surface roughness of MMO nanostructures increased. Calcination at 950 °C resulted in the formation of MMO nanoparticles. The optical properties of the MMO nanostructures were probed by UV-vis diffuse reflectance spectroscopy. The spectra varied depending on their dimensions and crystalline natures.     

Perpendicular magnetic anisotropy in 70 nm CoFe2O4 thin films fabricated on SiO2/Si(1 0 0) by the sol-gel method

Cobalt ferrite CoFe₂O₄ films were fabricated on SiO₂/Si(1 0 0) by the sol-gel method. Films crystallized at/above 600 °C are stoichiometric as expected. With increase of the annealing temperature from 600 °C to 750 °C, the columnar grain size of CoFe₂O₄ film increases from 13 nm to 50 nm, resulting in surface roughness increasing from 0.46 nm to 2.55 nm. Magnetic hysteresis loops in both in-plane and out-of-plane directions, at different annealing temperatures, indicate that the films annealed at 750 °C exhibit obvious perpendicular magnetic anisotropy. Simultaneously, with the annealing temperature increasing from 600 °C to 750 °C, the out of plane coercivity increases from 1 kOe to 2.4 kOe and the corresponding saturation magnetization increases from 200 emu/cm³ to 283 emu/cm³. In addition, all crystallized films exhibit cluster-like structured magnetic domains.     

Ultrasonic-assisted in situ synthesis and characterization of superparamagnetic Fe3O4 nanoparticles

Superparamagnetic Fe₃O₄ nanoparticles were synthesized via a modified coprecipitation method, and were characterized with X-ray diffraction (XRD), vibrating sample magnetometer (VSM), Zeta potential and FT-IR, respectively. The influences of different kinds of surfactants (sodium dodecyl benzene sulfonate, polyethyleneglycol, oleic acid and dextran), temperatures and pH values on the grain size and properties were also investigated. In this method, Fe³⁺ was used as the only Fe source and partially reduced to Fe²⁺ by the reducing agent with precise content. The following reaction between Fe³⁺, Fe²⁺ and hydroxide radical brought pure Fe₃O₄ nanoparticles. The tiny fresh nanoparticles were coated in situ with surfactant under the action of sonication. Comparing with uncoated sample, the mean grain size and saturation magnetization of coated Fe₃O₄ nanoparticles decrease from 18.4 nm to 5.9-9.0 nm, and from 63.89 emu g⁻¹ to 52-58 emu g⁻¹ respectively. When oleic was used as the surfactant, the mean grain size of Fe₃O₄ nanoparticles firstly decreases with the increase of reaction temperature, but when the temperature is exceed to 80 °C, the continuous increase of temperature resulted in larger nanoparticles. the grain size decreases gradually with the increasing of pH values, and it remains unchanged when the PH value is up to 11. The saturation magnetization of as-prepared Fe₃O₄ nanoparticles always decreases with the fall of grain size.     

Fe3O4/SiO2/Bi2WO6磁性复合光催化剂的制备及其光催化性能

钨酸铋(Bi₂WO₆),结构最简单的Aurivillius相化合物,是近期受到研究者关注的新型光催化材料。然而,光催化剂粉末在反应介质中难被回收,工业化应用成本较高。本文用三步方法合成了可回收的Fe₃O₄/SiO₂/Bi₂WO₆磁性复合光催化剂,通过溶剂热法合成具有磁性的Fe₃O₄,用溶胶凝胶法在Fe₃O₄表面覆盖SiO₂层,后将磁性颗粒与Bi₂WO₆纳米片相结合。光催化剂的形貌结构及性能通过XRD、SEM、PL、UV-vis进行表征测试。结果表明,直径约500 nm的Fe₃O₄微球附着在边长约500 nm的Bi₂WO₆纳米片的表面,SiO₂在两者之间起到了粘连作用。光催化剂Fe₃O₄/SiO₂/Bi₂WO₆对于罗丹明B的光降解活性较好,且有一定磁性,可以通过外加磁场将其从溶液中分离,有较大的应用潜力。     

Dielectric and microwave properties of ZrO2 doped CaO-SiO2-B2O3 ceramic matrix composites

The behavior of dielectric and microwave properties against sintering temperature has been carried out on CaO-SiO₂-B₂O₃ ceramic matrix composites with ZrO₂ addition. The results indicated that ZrO₂ addition was advantageous to improve the dielectric and microwave properties. X-ray diffraction (XRD) patterns show that the major crystalline β-CaSiO₃ and a little SiO₂ phase existed at the temperature ranging from 950 °C to 1050 °C. At 0.5 wt% ZrO₂, CaO-SiO₂-B₂O₃ ceramic matrix composites sintered at 1000 °C possess good dielectric properties: ?_r = 5.85, tan δ = 1.59 × 10⁻⁴ (1 MHz) and excellent microwave properties: ?_r = 5.52, Q · f = 28,487 GHz (11.11 GHz). The permittivity of Zr-doped CaO-SiO₂-B₂O₃ ceramic matrix composites exhibited very little temperature dependence, which was less than ±2% over the temperature range of −50 to 150 °C. Moreover, the ZrO₂-doped CaO-SiO₂-B₂O₃ ceramic matrix composites have low permittivity below 5.5 over a wide frequency range from 20 Hz to 1 MHz.     

Deposition and characterization of CrN/Si3N4 and CrAlN/Si3N4 nanocomposite coatings prepared using reactive DC unbalanced magnetron sputtering

Nanocomposite coatings of CrN/Si₃N₄ and CrAlN/Si₃N₄ with varying silicon contents were synthesized using a reactive direct current (DC) unbalanced magnetron sputtering system. The Cr and CrAl targets were sputtered using a DC power supply and the Si target was sputtered using an asymmetric bipolar-pulsed DC power supply, in Ar + N₂ plasma. The coatings were approximately 1.5 μm thick and were characterized using X-ray diffraction (XRD), nanoindentation, X-ray photoelectron spectroscopy and atomic force microscopy. Both the CrN/Si₃N₄ and CrAlN/Si₃N₄ nanocomposite coatings exhibited cubic B1 NaCl structure in the XRD data, at low silicon contents (< 9 at.%). A maximum hardness and elastic modulus of 29 and 305 GPa, respectively were obtained from the nanoindentation data for CrN/Si₃N₄ nanocomposite coatings, at a silicon content of 7.5 at.%. (cf., 24 and 285 GPa, respectively for CrN). The hardness and elastic modulus decreased significantly with further increase in silicon content. CrAlN/Si₃N₄ nanocomposite coatings exhibited a hardness and elastic modulus of 32 and 305 GPa, respectively at a silicon content of 7.5 at.% (cf., 31 and 298 GPa, respectively for CrAlN). The thermal stability of the coatings was studied by heating the coatings in air for 30 min in the temperature range of 400-900 °C. The microstructural changes as a result of heating were studied using micro-Raman spectroscopy. The Raman data of the heat-treated coatings in air indicated that CrN/Si₃N₄ and CrAlN/Si₃N₄ nanocomposite coatings, with a silicon content of approximately 7.5 at.% were thermally stable up to 700 and 900 °C, respectively.     

Combustion synthesis of CaSc2O4:Ce nano-phosphors in a closed system

The CaSc₂O₄:Ce³⁺ nano-phosphors were successfully prepared by a single-step combustion method at an ignition temperature as low as 200 °C in a closed autoclave using glycine as a fuel and PEG4000 as a dispersant. The samples were characterized by X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscope (TEM). The results revealed that CaSc₂O₄:Ce³⁺ nano-phosphors can be conveniently prepared at an ignition temperature as low as 200 °C, which was much lower than that in the ordinary combustion methods. The optimized ignition temperature was 220 °C. The CaSc₂O₄:Ce³⁺ nano-phosphors give a uniform particle size in the range of 15-20 nm. The low ignition temperature and the addition of PEG4000 dispersant play important roles in the formation of small sized nanoparticles. The as-prepared nano-phosphors were incompact aggregates, but highly dispersed nano-phosphors can be obtained after further ultrasonic treatment. The CaSc₂O₄:Ce³⁺ nano-phosphors give satisfactory luminescence characteristic benefiting from the closed circumstance, in which cerium atoms can be isolated from the oxidizing atmosphere and non-fluorescent Ce⁴⁺ ions can be ruled out. The present highly dispersed CaSc₂O₄:Ce³⁺ nano-phosphors with efficient fluorescence are promising in the field of biological labeling, and the present low temperature combustion method is facile and convenient and can be applied as a universal process for preparing non-aggregate oxide nano-phosphors, especially those being sensitive to air at high temperature.     

Complex impedance analysis of (Y2O3 + CeO2)-YCr0.5Mn0.5O3 composite NTC ceramics

Ceramic compositions based on (aY₂O₃ + bCeO₂)-0.4YCr_0.5Mn_0.5O₃ (a + b = 0.6) were prepared by conventional solid state reaction at 1200 °C, and sintered under air atmosphere at 1600 °C. For 0 ≤ a < 0.6, XRD patterns have shown that the major phases presented in the calcined powders are Y₂O₃, CeO₂ and orthorhombic perovskite YCr_0.5Mn_0.5O₃ phase, respectively. SEM and EDAX observations confirm the YCr_0.5Mn_0.5O₃ phases mostly exist at the grain, whereas the Y₂O₃ and CeO₂ phases mainly exist at the grain boundaries. Complex impedance analysis shows that, for 0 < a ≤ 0.6, single semicircular arc whose shape does not show any change with temperature. Nevertheless, for a = 0, two overlapping semicircular arcs are observed at and above 300 °C. The grain boundary properties exhibit thermistor parameters with a negative temperature coefficient characteristic. The relaxation behavior and conduction for the grain boundary could be due to a space-charge relaxation mechanism and oxygen vacancies, respectively.