Low temperature synthesis and optical properties of CaTiO3 nanoparticles from Ca(NO3)2·4H2O and TiO2 nanocrystals

Choosing low-melting-point Ca(NO₃)₂·4H₂O and high-reactive-activity TiO₂ nanocrystals as the raw materials, a simple and cost-effective route was developed for the synthesis of CaTiO₃ nanoparticles at 600 °C, which is much lower than that (about 1350 °C) used in the conventional solid state reaction methods. X-ray diffraction, energy dispersive X-ray spectroscopy and field emission scanning electron microscopy revealed the formation of orthorhombic phase CaTiO₃ nanoparticles with oxygen-deficiency at the surface. UV-vis absorption spectrum of the as-obtained CaTiO₃ nanoparticles displayed an absorption peak centered at around 325 nm (3.8 eV), together with a tail at lower energy side. Room temperature photoluminescence spectrum of the as-obtained CaTiO₃ nanoparticles upon laser excitation at 325 nm demonstrated a strong and broad visible light emission ranging from about 527 to 568 nm, which may be originated from the surface states and defect levels.     

Hydrothermal synthesis, characterization, photocatalytic activity and dye-sensitized solar cell performance of mesoporous anatase TiO2 nanopowders

Mesoporous anatase TiO₂ nanopowder was synthesized by hydrothermal method at 130 °C for 12 h. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), HRTEM, and Brunauer-Emmett-Teller (BET) surface area. The as-synthesized sample with narrow pore size distribution had average pore diameter about 3-4 nm. The specific BET surface area of the as-synthesized sample was about 193 m²/g. Mesoporous anatase TiO₂ nanopowders (prepared by this study) showed higher photocatalytic activity than the nanorods TiO₂, nanofibers TiO₂ mesoporous TiO₂, and commercial TiO₂ nanoparticles (P-25, JRC-01, and JRC-03). The solar energy conversion efficiency (η) of the cell using the mesoporous anatase TiO₂ was about 6.30% with the short-circuit current density (Jsc) of 13.28 mA/cm², the open-circuit voltage (Voc) of 0.702 V and the fill factor (ff) of 0.676; while η of the cell using P-25 reached 5.82% with Jsc of 12.74 mA/cm², Voc of 0.704 V and ff of 0.649.     

Nonaqueous sol-gel synthesis and growth mechanism of single crystalline TiO2 nanorods with high photocatalytic activity

In this paper, we report on a nonaqueous synthesis of single crystalline anatase TiO₂ nanorods by reaction between TiCl₄ and benzyl alcohol at a low temperature of 80 °C. The resulting samples were characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscopy, nitrogen adsorption, X-ray photoelectron spectrometry and UV-vis diffuse reflectance spectroscopy. We proposed that the TiO₂ nanorods were formed through an oriented attachment mechanism. More importantly, these single crystalline anatase TiO₂ nanorods exhibited significantly higher photocatalytic activities than commercial photocatalyst P25. This study provides an environmentally friendly and economic approach to produce highly active TiO₂ photocatalyst.     

Facile synthesis of mesoporous core-shell TiO2 nanostructures from TiCl3

The present study reports the synthesis and formation process of mesoporous core-shell TiO₂ nanostructures by employing a glucose-assisted solvothermal process using water-ethanol mixture as solvent and subsequent calcination process at 550 °C for 4 h. X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption analysis were used to investigate the structural properties of these nanostructures. By optimizing the preparation conditions, especially the contents of water and ethanol in the mixture solvent, mesoporous core-shell TiO₂ nanostructures were obtained. These mesoporous nanostructures have anatase phase and exhibit the superior photocatalytic activity. This synthesis route is facile due to the usage of stable and low-cost Ti precursor such as TiCl₃ and is thus applicable for large-scale production.     

Optimized microwave dielectric properties of Co- and Ca-substituted Mg0.6Zn0.4TiO3

The system of (1 − y)(Mg_0.6Zn_0.4)_1−xCo_xTiO₃-yCaTiO₃ was investigated to optimize its microwave dielectric properties by adopting appropriate contents of Co and Ca and by controlling sintering conditions. The effect of Co substitution was to enhance densification and Qf value, while the addition of CaTiO₃ resulted in increases of dielectric constant and TCF. As an optimal compositions, 0.93(Mg_0.6Zn_0.4)_0.95Co_0.05TiO₃-0.07CaTiO₃ successfully demonstrated a dielectric constant of 23.04, a Qf of 79,460 GHz and a TCF value of +1.4 ppm/°C after firing at a relatively lower sintering temperature of 1200 °C. The increase of sintering temperature beyond 1200 °C tended to degrade overall microwave dielectric properties presumably due to Zn volatilization as evidenced by the presence of a Zn-deficient phase (MgTi₂O₅) at 1400 °C. An attempt to establish the correlation between microstructure characteristics and dielectric properties was made in this dielectric system where the extensive range of firing temperature up to 1400 °C was evaluated.     

Dielectric properties of (1−x)(Mg0.95Co0.05)TiO3-xCaTiO3 ceramic system at microwave frequency

The microwave dielectric properties and the microstructures of the (1−x)MgTiO₃-xCaTiO₃ ceramic system were investigated. With partial replacement of Mg by Co, dielectric properties of the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramics can be promoted. The microwave dielectric properties are strongly correlated with the sintering temperature. At 1275°C, the 0.95(Mg_0.95Co_0.05)TiO₃-0.05CaTiO₃ ceramics possesses excellent microwave dielectric properties: a dielectric constant ε_r of 20.3, a Q×f value of 107 000 ( at 7 GHz) and a τ_f value of −22.8 ppm/°C. By appropriately adjusting the x value in the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramic system, zero τ_f value can be achieved. With x=0.07, a dielectric constant ε_γ of 21.6, a Q×f value of 92 000 (at 7 GHz) and a τ_f value of −1.8 ppm/°C was obtained for 0.93(Mg_0.95Co_0.05)TiO₃-0.07CaTiO₃ ceramics sintered at 1275°C for 4 h.     

Preparation and characterization of the TiO2 ultrafine particles by detonation method

Utilizing the raw materials of TiOSO₄, NaOH, NH₄NO₃ and RDX, the TiO₂ ultrafine particles were prepared under high pressure and high temperature by detonation method. The structure, composition and size distribution of the TiO₂ ultrafine particles were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results indicated the as-prepared TiO₂ ultrafine particles exhibited spherical-like grains and that the average size of particles was 25 ± 5 nm. After being heated at 700 °C for 1 h, TiO₂ particles have entirely completed the anatase-rutile phase transition, which means that detonation method can effectively enhance the anatase-rutile phase transition by lowering the transition temperature. The size of TiO₂ nanoparticles can be effectively controlled because the as-prepared nanoparticles do not have enough time to grow to large and perfect crystallites during the detonation process.     

Photoluminescence from terbium doped silica-titania prepared by a sol-gel method

Terbium doped (0.5 at.%) TiO₂-SiO₂ (30%/70%) was prepared by a sol-gel method. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the powder calcined at two different temperatures. At a low temperature of 550 °C an amorphous phase was obtained, but at a higher temperature of 1000 °C, the anatase TiO₂ phase was crystallized in the amorphous SiO₂ phase. Green photoluminescence from ultraviolet excitation was detected after heating to either temperature, but the amorphous sample heated to 550 °C exhibited a higher intensity. X-ray diffraction and photoluminescence excitation data are discussed to explain these observations.     

Characterization of exfoliated/delamination kaolinite

A novel and facile approach for the preparation of exfoliated/delamination kaolinite was reported in this study. Kaolinite was mechanochemically activated by grinding with dimethylsulfoxide in a globe mill for different periods of time, and then the activated samples were treated for several hours at 120 °C to obtain the precursors of kaolinite. The resulting materials were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The experimental data indicated that the clay layers were well exfoliated/delamination under mechanochemical effect in a significantly short intercalation time. The expansion of the basal spacing (d_0 0 1) of raw kaolinite by 0.40 nm pointed out that the hydrogen bonds between adjacent kaolinite layers were partially broken as a result of the intercalation with dimethylsulfoxide.     

Effect of anionic surfactant on vaterite CaCO3

Calcium carbonate (CaCO₃) crystals with various shapes have been synthesized by aging calcium chloride and urea hybrid solution containing sodium dodecylsulfonate (SDSN) or sodium dodecylbenzenesulfonate (SDBS) in a 90 °C bath. The effects of SDSN and SDBS on the morphology and polymorph of precipitated CaCO₃ are investigated with the help of scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectrometer and X-ray diffraction (XRD). Flower-like vaterite changes from monolayer to multilayer structure with the increase of SDSN concentration. While the crystal shape changes from plate-like, through rose-shaped, hat-like, to bicone-like as the concentration of SDBS is increased.     

Si-substituted hydroxyapatite nanopowders: Synthesis, thermal stability and sinterability

Synthetic hydroxyapatites incorporating small amounts of Si have shown improved biological performances in terms of enhanced bone apposition, bone in-growth and cell-mediated degradation.This paper reports a systematic investigation on Si-substituted hydroxyapatite (Si 1.40 wt%) nanopowders produced following two different conventional wet methodologies: (a) precipitation of Ca(NO₃)₂·4H₂O and (b) titration of Ca(OH)₂. The influence of the synthesis process on composition, thermal behaviour and sinterability of the resulting nanopowders is studied.Samples were characterised by electron microscopy, induced coupled plasma atomic emission spectroscopy, thermal analysis, infrared spectroscopy, N₂ adsorption measurements, X-ray diffraction and dilatometry. Semicrystalline Si-substituted hydroxyapatite powders made up of needle-like nanoparticles were obtained, the specific surface area ranged between 84 and 110 m²/g. Pure and Si-substituted hydroxyapatite nanopowders derived from Ca(NO₃)₂·4H₂O decomposed around 1000 °C. Si-substituted hydroxyapatite nanopowders obtained from Ca(OH)₂ were thermally stable up to 1200 °C and showed a distinct decreased thermal stability with respect to the homologous pure sample. Si-substituted hydroxyapatites exhibited higher sintering temperature and increased total shrinkage with respect to pure powders. Nanostructured dense ceramics were obtained by sintering at 1100 °C Si-substituted hydroxyapatites derived from Ca(OH)₂.     

Rapid formation of lead magnesium niobate-based ferroelectric ceramics via a high-energy ball milling process

Pyrochlore-free nano-sized 0.90Pb(Mg_1/3Nb_2/3)O₃(PMN)-0.10PbTiO₃(PT) and 0.65PMN-0.35PT powders were synthesized from oxides via a high-energy ball milling process. Single perovskite phase PMN-PT were readily formed from the oxide mixture after milling for only 2 h. The grain size calculated from X-ray diffraction (XRD) patterns of all samples is about 20 nm, which is in agreement with the observation from scanning electron microscopy (SEM) (20-50 nm). PMN-PT ceramics were obtained by sintering the milled powders at temperature from 1000 to 1100°C for 2 h. The dielectric, ferroelectric properties of the PMN-PT ceramics derived from the synthesized powders were comparable with the reported results in the literature.     

Microstructural and mechanical properties evolutions of plasma transferred arc deposited Norem02 hardfacing alloy at high temperature

Plasma-transferred-arc welded Norem02, an iron-based hard-facing alloy, was characterised. Its microstructure and chemical composition were investigated using optical microscopy, scanning electron microscopy (with electron probe microanalysis), electron backscattering diffraction, and X-ray diffraction. The microstructure of the as-deposit alloy consists of a dendritic austenite structure with ferrite islets at dendrites centres, with an interdendritic eutectic region containing austenite, M₇C₃ and M₂₃C₆ carbides and zones containing Mo-rich precipitates. Tensile behaviour of Norem02 was characterised and completed by dilatometry tests in welding process temperature range. No significant phase transformation was detectable during mechanical testing. Different heat treatment cycles of ageing at high temperatures (until 1100 °C) were carried out for different durations. The microstructure of Norem02 heated at 1100 °C was not significantly affected by a short time (15 s) treatment whereas changes were observed for longer durations (2 h), although hardness remains almost unchanged.This work tends to demonstrate that for this alloy metallurgical evolution during the welding process has very little influence on mechanical properties.     

Formation of SrTiO3 from Sr-oxalate and TiO2

SrTiO₃ powder has been prepared from Sr-oxalate and TiO₂ precursors, instead of using titanyl-oxalate. Sr-oxalate was precipitated from nitrate solution onto the surface of suspended TiO₂ powders. Crystallization of SrTiO₃ from the precursor was investigated by TGA, DTA and XRD analysis. It is evident that precursor, upon heating, dehydrates in two stages, may be due to the presence of two different types of Sr-oxalate hydrates. Dehydrated precursor then decomposes into SrCO₃ and TiO₂ mixture. Decomposition of SrCO₃ and simultaneous SrTiO₃ formation occur at much lower temperature, from 800 °C onwards, due to the fine particle size of the SrCO₃ and presence of acidic TiO₂ in the mixture. The precursor completely transforms into SrTiO₃ at 1100 °C. About 90 nm size SrTiO₃ crystallites are produced at 1100 °C/1 h, due to the lower calcination temperature and better homogeneity of the precursor.     

Synthesis and characterization of Zn-B-Si-O nano-composites and their doped BaTiO3 ceramics

We synthesized Zn-B-Si-O (ZBSO) nano-composites via sol-gel process, and then used them to dope BaTiO₃ ceramics. The ZBSO nano-composites and their ceramics were characterized by means of thermogravimetric, Fourier-transform infrared, and X-ray diffraction methods, and using scanning and transmission electron microscopy. We also characterized the dielectric properties of the ceramics. The results indicated that the ZBSO nano-composites were nanometer-scale powders with an amorphous structure. The particle size of the powders increased with increasing pH value, but initially decreased and then increased with increasing calcining temperature. At pH about 2 and with calcining at 400 °C, the nano-composites attained minimum particle size (about 30 nm). The sintering temperature of the BaTiO₃ ceramics could be reduced to 1100 °C by adding 5 wt% of the ZBSO nano-composites. Uniform, fine-grained BaTiO₃ ceramics with a high permittivity (?_r = 2946 and ?_max = 5072) were obtained by adding nano-composites; these properties were superior to the ZBSO glass doped BaTiO₃ ceramics.     

Hydrothermal synthesis and characterization of TiO2 nanorod arrays on glass substrates

Large-scale, well-aligned single crystalline TiO₂ nanorod arrays were prepared on the pre-treated glass substrate by a hydrothermal approach. The as-prepared TiO₂ nanorod arrays were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. X-ray diffraction results show that the main phase of TiO₂ is rutile. Scanning electron microscopy and transmission electron microscopy results demonstrate that the large-scale TiO₂ nanorod arrays grown on the pre-treated glass substrate are well-aligned single crystal and grow along [0 0 1] direction. The average diameter and length of the nanorods are approximately 21 and 400 nm, respectively. The photocatalytic activity of TiO₂ nanorod arrays was investigated by measuring the photodegradation rate of methyl blue aqueous solution under UV irradiation (254 nm). And the results indicate that TiO₂ nanorod arrays exhibit relatively higher photocatalytic activity.     

Synthesis of well-crystallized birnessite using ethylene glycol as a reducing reagent

Well-crystallized birnessite sheets containing K⁺ in the interlayers have been prepared using KMnO₄, ethylene glycol and KOH by microwave heating at 90 °C for 10 min. Ethylene glycol was used as a reducing agent. The effect of KOH concentration on the formation of birnessite was studied. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TG), differential scanning calorimetric analysis (DSC) and Fourier transform infrared (FTIR). Birnessites were converted to cryptomelane upon heating at 400-800 °C and completely collapsed to form Mn₃O₄ at 1000 °C.     

Low-temperature synthesis and characterization of yttrium-gallium garnet Y3Ga5O12 (YGG)

To obtain yttrium-gallium garnet (Y₃Ga₅O₁₂, YGG) a simple “chimie douce” method has been developed. This sol-gel method yielded excellent starting gel precursor for the fabrication of YGG phase, which could be used as host material for optical applications. The pattern of X-ray diffraction analysis of the ceramic sample sintered for 10 h at 1000 °C showed the formation of monophasic Y₃Ga₅O₁₂ phase. The phase transformations, composition and micro-structural features in the gels and polycrystalline sample were studied by thermoanalytical methods (TGA/DTA), powder X-ray diffraction analysis (XRD), infrared spectroscopy (IR) and scanning electron microscopy (SEM). The quality of the resulting products (homogeneity, crystallisation temperature, grain size, grain size distribution, etc.) is discussed.     

Direct diffusion bonding of Ti3SiC2 and Ti3AlC2

Two typical layered ternary compounds, Ti₃SiC₂ and Ti₃AlC₂, were joined directly by solid-state diffusion bonding method. By various bonding tests at 1100-1300 °C for 30-120 min under 10-30 MPa, and characterizing the microstructure and diffusion reactive phases of the joints by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and X-ray diffraction (XRD), the optimal condition for direct joining of Ti₃SiC₂ and Ti₃AlC₂ was obtained. Strong joints of Ti₃SiC₂/Ti₃AlC₂ can be achieved via diffusion bonding, which is attributed to remarkable interdiffusion of Si and Al at the joint interface. The shear strength of the Ti₃SiC₂/Ti₃AlC₂ joints was determined.     

Biomolecule-assisted synthesis of ZnS nanocorals and open-benzene ring in supercritical carbon dioxide

The nanostructured ZnS of cubic nanocorals and open-benzene ring has been synthesized by the biomolecule-assisted method in mixture of supercritical carbon dioxide and water as reaction medium at 150 °C and 28 MPa. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, photoluminescence spectrum of sample were characterized. The sodium tripoly phosphate and CO₂ as well as high-pressure condition might be the key factors for formation of the particular morphologies and nanostructures of ZnS. This synthesis method could be employed for preparation of other semiconductor nanomaterials.