Synthesis and characterization of pure anatase TiO<Subscript>2</Subscript> nanoparticles

Pure anatase TiO₂ nanoparticles were synthesized by microwave assisted sol–gel method and further characterized by powder X-ray diffraction (XRD), energy dispersive x-ray analysis (EDAX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV–Visible spectrophotometer, SEM images showed that TiO₂ nanoparticles were porous structure. The XRD patterns indicated that TiO₂ after annealed at 300 °C for 3 h was mainly pure anatase phase. The crystallite size was in the range of 20–25 nm, which is consistent with the results obtained from TEM images. Microwave heating offers several potential advantages over conventional heating for inducing or enhancing chemical reactions.     

Formation of TiO<Subscript>2</Subscript> nanotubes by thermal decomposition of poly(vinyl alcohol)-titanium alkoxide hybrid nanofibers

Anatase type TiO₂ nanotubes were formed by calcination of poly(vinyl alcohol)-Ti alkoxide hybrid precursor nanofibers in air. The outer and inner diameters of the TiO₂ nanotubes calcined at 500 °C for 5 h were ca. 440 nm and ca. 270 nm, respectively. The specific surface area of the TiO₂ nanotubes was 38.8 m²/g, and the existence of mesopores (average pore diameter, 14.8 nm) on the nanotube wall was indicated by the nitrogen adsorption isotherm (−196 °C). The photocatalysis of the TiO₂ nanotubes was superior to that of commercially available anatase type TiO₂ nanoparticles.     

Synthesis of nano-MoS<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> composite and its catalytic degradation effect on methyl orange

A nano-MoS₂/TiO₂ composite was synthesized in H₂ atmosphere by calcining a MoS₃/TiO₂ precursor, which was obtained via a quick deposition of MoS₃ on anatase nano-TiO₂ under a strong acidic condition. The obtained nano-MoS₂/TiO₂ composite was characterized by X-ray diffraction spectroscopy, Brunauer–Emmett–Teller (BET) surface area, scanning electron microscopy, high-resolution transmission electron microscopy, energy-dispersive spectrometry, ultraviolet–visible spectroscopy, and Fourier transform infrared spectroscopy. The results show that the composite had a high BET surface area because of its small size and irregularly layered structure. MoS₂ in the composite was composed of typical layered structures with thicknesses of 2–8 nm and lengths of 10–40 nm. The composite contained a wide and intensive absorption at 400–700 nm, which is in the visible light region, and presented a positive catalytic effect on removing methyl orange from the aqueous solution. The catalytic activity of the composite was influenced by the initial concentration of methyl orange, the amount of the catalyst, the pH value, and the degradation temperature. In addition, the composite catalyst could be regenerated and repeatedly used via filtration three times. The deactivating catalyst could be reactivated after catalytic reaction by heating at 450 °C for 30 min in H₂.     

Functionalization of electrospun magnetically separable TiO<Subscript>2</Subscript>-coated SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript> nanofibers: strongly effective photocatalyst and magnetic separation

Magnetically separable TiO₂-coated SrFe₁₂O₁₉ electrospun nanofibers were obtained successfully by means of sol–gel, electrospinning, and coating technology, followed by heat treatment at 550–650 °C for 3 h. The average diameter of the electrospun fibers was 500–600 nm. The fibers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM). The optimized calcining temperature was determined by XRD and the analysis of decolorizing efficiency of methylene blue (MB) under UV–vis irradiation. The photocatalytic activity of the TiO₂-coated SrFe₁₂O₁₉ fibers was investigated using ultraviolet–visible absorbance by following the photooxidative decomposition of a model pollutant dye solution, MB in a photochemical reactor. In contrast to pure TiO₂ fibers, the TiO₂-coated SrFe₁₂O₁₉ fibers have higher absorption in 250–750 nm wavelength regions. The presence of SrFe₁₂O₁₉ not only broadened the response region of visible-light, but also enhanced the absorbance for UV light. The decolorizing efficiency of MB under UV–vis irradiation was up to 98.19%, which was a little higher than that of Degussa P25 (97.68%). Furthermore, these fibers could be recollected easily with a magnet in a photocatalytic process and had effectively avoided secondary pollution of treated water.     

Effect of temperature and time on solvothermal synthesis of tetragonal BaTiO<Subscript>3</Subscript>

Tetragonal BaTiO₃ nanoparticles are synthesized via solvothermal route in an ethanol water mixture. Ba(OH)₂·8H₂O is used as Ba precursor and TiO₂ (P25 Degussa ∼25 nm, 30% anatase, 70% rutile) is used as Ti precursor in the Ba : Ti molar ratio 2 : 1. Effect of temperature and time study on solvothermal synthesis of BaTiO₃ revealed that a moderate reaction temperature i.e. 185°C and longer reaction time favour tetragonal phase stabilization. Dissolution–precipitation appears to be the transformation mechanism for the crystallization of BaTiO₃ from particulate TiO₂ precursor.     

Thermal Conductivity and Viscosity Measurements of Water-Based TiO<Subscript>2</Subscript> Nanofluids

In this study, the thermal conductivity and viscosity of TiO₂ nanoparticles in deionized water were investigated up to a volume fraction of 3% of particles. The nanofluid was prepared by dispersing TiO₂ nanoparticles in deionized water by using ultrasonic equipment. The mean diameter of TiO₂ nanoparticles was 21 nm. While the thermal conductivity of nanofluids has been measured in general using conventional techniques such as the transient hot-wire method, this work presents the application of the 3ω method for measuring the thermal conductivity. The 3ω method was validated by measuring the thermal conductivity of pure fluids (water, methanol, ethanol, and ethylene glycol), yielding accurate values within 2%. Following this validation, the effective thermal conductivity of TiO₂ nanoparticles in deionized water was measured at temperatures of 13 °C, 23 °C, 40 °C, and 55 °C. The experimental results showed that the thermal conductivity increases with an increase of particle volume fraction, and the enhancement was observed to be 7.4% over the base fluid for a nanofluid with 3% volume fraction of TiO₂ nanoparticles at 13 °C. The increase in viscosity with the increase of particle volume fraction was much more than predicted by the Einstein model. From this research, it seems that the increase in the nanofluid viscosity is larger than the enhancement in the thermal conductivity.     

Synthesis and characterization of anatase and rutile TiO2 nanorods by template-assisted method

Well-aligned anatase and rutile TiO₂ nanorods and nanotubes with a diameter of about 80–130 nm have successfully been fabricated via sol-gel template method. The prepared samples were characterized by using thermogravimetric (TG) and differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). The XRD results indicated that the TiO₂ nanorods were crystallized in the anatase and rutile phases, after annealing at 400–800 °C for different periods of time from 0.2 to 10 h.     

Phase transformation and precipitation behavior of niobium component out of niobium-doped anatase-type TiO<Subscript>2</Subscript> nanoparticles synthesized via hydrothermal crystallization

The precipitation behavior of niobium component out of niobium-doped anatase-type TiO₂ and structural change in the course of heating were investigated. The samples were directly formed under hydrothermal conditions at 240 °C for 5 h in the presence of aqueous ammonia via crystallization from co-precipitates that were obtained from precursor solutions of TiOSO₄ and NbCl₅. The as-prepared niobium-doped anatase-type titania nanoparticles showed bluish color and absorption in the visible region, which was confirmed to be due to the presence of Ti(III) in the solid solutions using electron paramagnetic resonance measurement. The niobium-doped anatase-type titania existed stably without an appearance of any other phases after heating up to 500 °C for 1 h. In the course of heating at 500–800 °C, continual and clear decrease in the lattice parameters a ₀ and c ₀ of the anatase was observed, which was followed by the precipitation of Nb₂O₅ and TiNb₂O₇ out of the niobium-doped anatase, but the anatase phase was maintained without anatase-to-rutile phase transformation up to 850–1,000 °C. The anatase-to-rutile phase transformation was gradually retarded when the niobium content increased.     

Dielectric properties of Na<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript>K<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>NbO<Subscript>3</Subscript> in orthorhombic phase

Pellets of ceramic Na_1−xK_xNbO₃ (x = 0, 0.2 and 0.5), were prepared by conventional solid-state reaction method. Prepared samples were characterized using XRD and SEM. The frequency and temperature variation of dielectric constant, loss tangent and dielectric conductivity of prepared samples were measured in the frequency range from 10 KHz-1 MHz, and in the temperature range from 50–250°C for x = 0.2 and 0.5, and between 50 and 480°C for x = 0 compositions. It was observed that the dielectric constant and loss tangent decrease, and conductivity increases with increasing frequency. Near the transition temperature the material shows anomalous behaviour for the observed properties, and the peaks of dielectric constant and loss tangent were observed shifting towards lower temperature with increasing frequency.     

Hydrothermal synthesis of hemisphere-like F-doped anatase TiO<Subscript>2</Subscript> with visible light photocatalytic activity

Hemisphere-like F-doped anatase TiO₂ has been synthesized by hydrothermal treatment of TiF₄ aqueous solution in the presence of starch at 130 °C for 10 h, and then calcined at 450 °C for 2.5 h in air. The as-synthesized product has been investigated by photocatalytic reaction test and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV–Vis diffuse reflectance spectra (DRS). The results showed that fluorine was successfully doped into the TiO₂ hemispheres. The F-doped TiO₂ hemispheres showed high visible light activity in degradation of acid orange II, which could be attributed to the creation of oxygen vacancies and good crystallinity.     

Photocatalytic reduction of methylene blue by TiO2 nanotube arrays: effects of TiO2 crystalline phase

TiO₂ nanotube arrays were synthesized by anodization of Ti metal sheets followed by thermal annealing at elevated temperatures from 400 to 600 °C. Scanning electron microscopic measurements showed that dense arrays of nanotubes were produced with the inner diameter about 100 nm, wall thickness 35 nm, and length about 10 μm. X-ray diffraction measurements showed that the as-prepared nanotubes were largely amorphous, whereas thermal annealing led to the formation of well-defined anatase crystalline phase. More interestingly, at 470 °C, the brookite crystalline phase also started to emerge, which became better defined at 500 °C and disappeared eventually at higher temperatures, a phenomenon that has not been observed previously in TiO₂ nanotube arrays prepared by anodization. The impacts of the TiO₂ nanocrystalline structure on the photocatalytic activity were then examined by using the reduction of methylene blue in water as an illustrating example. Upon exposure to UV lights, the visible absorption profiles of methylene blue exhibited apparent diminishment. Based on these spectrophotometric measurements, the corresponding pseudo-first-order rate constant was estimated, and the sample thermally annealed at 500 °C was found to exhibit the highest activity. The strong correlation between the TiO₂ crystalline characteristics and photocatalytic performance suggests that the synergistic coupling of the anatase and brookite crystalline domains led to effective charge separation upon photoirradiation and hence improved photocatalytic activity, most probably as a consequence of the vectorial displacement at the nanoscale junctions between these crystalline grains that impeded the dynamics of electron–hole recombination. These results demonstrate the significance of nanoscale engineering in the manipulation of oxide photocatalytic performance.     

Phase transformations in the TiO<Subscript>2</Subscript>-NiO system

The anatase-rutile phase transition in fine-particle TiO₂-NiO oxides has been studied using physicochemical characterization techniques (X-ray diffraction, differential thermal analysis, and mass spectrometry). The results demonstrate that NiO additions considerably increase the rate of the anataserutile polymorphic transformation. Nickel titanate formation depends on the procedures used to prepare both titanium dioxide and nickel oxide. In the temperature range 700–850°C, the anatase to rutile phase transition prevents nickel titanate formation.     

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.     

Microstructure and H<Subscript>2</Subscript>S gas sensing properties of nanocrystalline perovskite-type La<Subscript>0.6</Subscript>Co<Subscript>0.4</Subscript>Mn<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>O<Subscript>3</Subscript>

Nanocrystalline La_1−x Co _x Mn_1−y Ni _y O₃ (x = 0.2 and 0.4; y = 0.1, 0.3, and 0.5) thick films sensors prepared by sol–gel method were studied for their H₂S gas sensitivity. The structural and morphological properties have been carried out by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Average particle size estimated from XRD and TEM analyses was observed to be 30–35 nm. The gas response characteristics were found to depend on the dopants concentration and operating temperature. The maximum H₂S gas response of pure LaMnO₃ was found to be at 300 °C. In order to improve the gas response, material doped with transition metals Co and Ni on A- and B-site, respectively. The La_0.6Co_0.4Mn_0.5Ni_0.5O₃ shows high response towards H₂S gas at an operating temperature 250 °C. The Pd-doped La_0.6Co_0.4Mn_0.5Ni_0.5O₃ sensor was found to be highly sensitive to H₂S at an operating temperature 200 °C. The gas response, selectivity, response time and recovery time were studied and discussed.     

Electrical and thermal properties of PTFE-Sr<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript> composites

A new polymer-ceramic composite was prepared using PTFE and low loss Sr₂ZnSi₂O₇. The dielectric properties of the composite were studied in the microwave and radiofrequency ranges. The relative permittivity (ε_r) and dielectric loss (tan δ) increased with the filler loading from 0.10 to 0.50 volume fractions (v_f). The observed values of ε_r, thermal conductivity and coefficient of thermal expansion (CTE) were compared with the corresponding theoretical predictions. The ability of the composite towards moisture absorption resistance was studied as a function of filler loading. It was also found that the variation of ε_r was less than 2% in the temperature range 25–90 °C, at 1 MHz. For a filler content of 0.50 v_f, the PTFE/Sr₂ZnSi₂O₇ composite exhibited ε_r = 4.4_, tan δ = 0.003 (at 4–6 GHz), CTE = 38.3 ppm/°C, thermal conductivity = 2.1 W/mK and moisture absorption = 0.09 wt%.     

Enhanced thermal stability in K<Subscript>2</Subscript>O-metakaolin-based geopolymer concretes by Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and SiO<Subscript>2</Subscript> fillers addition

Based on the principle of stability of geopolymer gel as refractory binder, a geopolymeric paste in the K₂O–Al₂O₃–SiO₂ system was developed and used to produce refractory concretes by adding various amount of α-quartz sand (grain size in the range 0.1 μm to 1 mm) and fine powder alumina (grain size in the range 0.1–100 μm). The consolidated samples were characterized before and after sintering using optical dilatometer, DSC, XRD and SEM. The total shrinkage in the range of 25–900 °C was less than 3%, reduced with respect to the most diffused potassium or sodium based geopolymer systems, which generally records a >5% shrinkage. The maximum shrinkage of the basic geopolymer composition was recorded at 1000 °C with a 17% shrinkage which is reduced to 12% by alumina addition. The temperature of maximum densification was shifted from 1000 °C to 1150 or 1200 °C by adding 75 wt% α-quartz sand or fine powder alumina respectively. The sequences of sintering of geopolymer concretes could be resumed as dehydration, dehydroxylation, densification and finally plastic deformation due to the importance of liquid phase. The geopolymer formulations developed in this study appeared as promising candidates for high-temperature applications: refractory, fire resistant or insulating materials.     

Formation behavior of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> from CaTiO<Subscript>3</Subscript>, CuO and TiO<Subscript>2</Subscript>

The formation behavior of CaCu₃Ti₄O₁₂ (CCTO) had been investigated via solid state reaction from CaTiO₃, CuO and TiO₂ powders. In the temperature range from 750 to 1,200 °C, the reaction sequence was traced by XRD, and the microstructure evolution of calcined powders was also investigated by SEM. CCTO began to form owing to the reaction between CaTiO₃, CuO and TiO₂ at around 850 °C, and became the major phase at 1,000 °C. Finally, the single phase CCTO was obtained at 1,150 °C. However, CCTO was decomposed at CaTiO₃, CuO and TiO₂ when the temperature increased to 1,200 °C. In addition, no other intermediate phases occurred in the synthesized process. The formation behaviors indicated that CaTiO₃ prevented the formation and growth of CCTO.     

Formation of Li<Superscript>+</Superscript> superionic crystals from the Li<Subscript>2</Subscript>S–P<Subscript>2</Subscript>S<Subscript>5</Subscript> melt-quenched glasses

The 70Li₂S·30P₂S₅ (mol%) glass was prepared by the melt quenching method and the glass–ceramic electrolytes were obtained by heating the prepared glass over crystallization temperatures. The superionic metastable Li₇P₃S₁₁ crystal was formed by heating the glass in the temperature range from 280 and 360 °C. The conductivity of the glass–ceramics was enhanced by the precipitation and growth of the Li₇P₃S₁₁ crystal, and the highest conductivity of 4.1 × 10⁻³ S cm⁻¹ at room temperature was achieved in the glass–ceramic heated at 360 °C for 1 h. The Li₇P₃S₁₁ crystal changed into the thermodynamically stable phase such as the Li₄P₂S₆ crystal with further increasing heat treatment temperature and holding time, resulting in lowering conductivities of the glass–ceramics.     

Dielectric and impedance spectroscopy study of Ba<Subscript>0.8</Subscript>Bi<Subscript>2.133</Subscript>Nb<Subscript>1.6</Subscript>Ta<Subscript>0.4</Subscript>O<Subscript>9</Subscript> ferroelectric ceramics,prepared by chemical route

Nanocrystalline ceramic powder of Ba_0.8Bi_2.133Nb_1.6Ta_0.4O₉ was synthesized by chemical precursor decomposition method. The single-phase formation of the compound was confirmed using an X-ray diffraction technique and was found to be a tetragonal phase at room temperature. Average crystallite size and particle size were found to be 41 and 48.5 nm, which were analyzed through XRD and TEM respectively. The dielectric constant and tangent loss were measured in the frequency range 1 kHz–1 MHz after sintering the sample at 900 °C for 4 h. The polarization behavior was studied at an applied voltage of 6.2 kV/cm. Electrical properties of the material were investigated using complex impedance spectroscopy (CIS) technique, which revealed the presence of both grain and grain-boundary effects in the materials, which is also evidenced from the scanning electron microscope image. Grain conductivity indicated Arrhenius-type thermally activated process. AC conductivity spectrum obeys Jonscher’s universal power law. The electric modulus analysis suggests the possibility of hopping mechanism for electrical processes in the system with a non-debye type relaxation, which is supported by the impedance data.     

Temperature-controlled assembly and morphology conversion of CoMoO<Subscript>4</Subscript>·3/4H<Subscript>2</Subscript>O nano-superstructured grating materials

The regular and homogeneous single-crystal CoMoO₄·3/4H₂O nanorods, with the diameters ca. 100–300 nm and lengths ca. 8–15 μm, have been successfully prepared by a simple and facile precipitation method. Their morphology conversion from broom-like to cage-like structure has been firstly reported through controlling the reaction temperature. The broom-like microbunches were obtained at 50 °C while at 80 °C, dispersive nanorods can be prepared. As the temperature reached 90 °C, the morphology of the products converted to cage-like microspheres. SEM results show that the reaction temperature has a critical role in both the formation of the products and their morphologies. The UV–visible diffuse reflectance absorbance spectra of the products display two intense, broad absorbance bands cover almost the whole ultraviolet and visible region except for a narrow region around 450 nm, which is in the region for purple light. Based on the experimental results, a possible formation mechanism was also proposed. The synthesis strategy is simple, facile, mild, and has a good reproducibility. The as-prepared products may have potential applications in optics, catalysis, and grating materials.