Antimony doping effect on barium titanate structure and electrical properties

Nanopowders of pure and antimony doped barium titanate (BaTiO₃-BT) were synthesized by polymeric precursors method based on Pechini process. Obtained powders were pressed and sintered at 1300 °C for 8 h. XRD analysis showed the formation of cubic crystal structure in all nanopowders and tetragonal in BT ceramics. The influence of antimony concentration on structure change, grain size reduction and microstructure development was analyzed. Dielectric behavior of pure and antimony doped ceramics was studied as a function of temperature and frequency. The significant dielectric properties modification as a consequence of doping with different antimony concentration was noticed. The electrical resistivity measurements pointed out that antimony concentration influenced also on materials change from insulator to semiconductor.     

The effect of the hydrothermal synthesis variables on barium titanate powders

In this work, the influence of (a) Ba excess in the starting hydrothermal mixture with TiO₂, (b) hydrothermal reaction temperature, and (c) washing cycles on the hydrothermal synthesis of barium titanate (BaTiO₃) were investigated to assess their relative contributions to the final characteristics of the sintered oxide. BaTiO₃ cake was prepared by hydrothermal synthesis at 150 °C and 180 °C using BaOH₂·8H₂O and TiO₂·xH₂O as starting hydrothermal mixture with an excess of Barium (+1 Ba mol% and +2 Ba mol%). The obtained BaTiO₃ cake was washed several times from 0 to 14 (W_n<15) using simple de-ionized water and then sintered at 1120 °C for 3 h. All considered hydrothermal syntheses variables strongly contribute to the final characteristics of the sintered BaTiO₃ powders in terms of Ba²⁺/Ti⁴⁺ molar ratio, crystalline structure and mean particle size. In particular, it is clear from these experiments that the removal of the unfavorable barium salts from BaTiO₃ cake by long washing cycles before final calcination is a critical step in the hydrothermal synthesis of BaTiO₃.     

Hydrothermal synthesis and formation mechanism of tetragonal barium titanate in a highly concentrated alkaline solution

Tetragonal cube-shaped barium titanate (BaTiO₃) was produced by the hydrothermal treatment of a peroxo-hydroxide precursor, a single-source amorphous barium titanate precursor, in a highly concentrated sodium hydroxide solution. Phase pure barium titanate with cube-shaped morphology and particle-sizes in the 0.2–0.5 µm range were formed at temperatures above 80 °C. Also, the cube-shaped morphology of the BaTiO₃ product was preceded by spherical- and plate-like morphologies with, respectively, a Ti-excess and Ba-excess. Coinciding with these morphological observations, changes in the reaction product were also observed. The formation of crystalline BaTiO₃ proceeded alongside secondary BaTi₂O₅ and Ba₂TiO₄ phases. These secondary phases disappeared as the reaction time was increased leaving only BaTiO₃ as the sole reaction product. Kinetic analysis of the formation of hydrothermal BaTiO₃ crystallization by the Johnson-Mehl-Avrami method showed that BaTiO₃ crystallization is a homogeneous dissolution-precipitation reaction. The mechanism is governed by nucleation and growth in the beginning of the reaction and dissolution-precipitation dominating throughout the hydrothermal reaction process.     

Synthesis of calcium copper titanate ceramics via the molten salts method

CaCu₃Ti₄O₁₂ has a giant dielectric constant of up to 10⁴ at room temperature and has great potential for various technological applications. In this work, CaCu₃Ti₄O₁₂ ceramic powder was synthesized by heating a stoichiometric amount of CaCO₃, CuO and TiO₂ in molten NaCl–KCl and Na₂SO₄–K₂SO₄, respectively. The synthesis temperature was decreased from 1000 °C (required by conventional solid-state reactions) to 750 °C for NaCl–KCl or to 850 °C for Na₂SO₄–K₂SO₄. The flux type has a larger influence on the phase compositions and morphology of the resultant powders than the synthesis temperature does. The dielectric constant of the resulting ceramics is more than 10⁴ over the wide frequency range from 100 Hz to 100 kHz. The dielectric loss tangent of the resulting ceramics is lower than 0.2 in the frequency range from 100 Hz to 100 kHz. The dielectric behavior of both samples is similar to the results obtained for CaCu₃Ti₄O₁₂ ceramics that were synthesized by the sol–gel method.     

Low-temperature synthesis of ZnNb2O6 powders via hydrothermal method

ZnNb₂O₆ powder was successfully synthesized via hydrothermal method with Nb₂O₅ and Zn(NO₃)₂·6H₂O as raw materials and cyclohexane as solvent. Phase composition, morphology, and chemical composition were determined via a combination of XRD, SEM, TEM and EDS techniques. The effects of synthesis temperature and reaction time on phase composition and particle morphology were investigated in this paper. The results showed that fine ZnNb₂O₆ powders could be obtained at a hydrothermal temperature of 190 °C or above under different reaction time.     

A comparative study of the synthesis of nanocrystalline Yttrium Aluminium Garnet using sol-gel and co-precipitation methods

Nanocrystalline yttrium aluminium garnet (nYAG) powder has been synthesized via sol-gel and co-precipitation methods using nitrate precursors. Thermal evolution and crystallisation kinetics of both the methods were investigated. The optimised calcination condition for the formation of nYAG was also examined. It was found that a complete transformation to nYAG was observed at 925 °C/2 h and 1000 °C/1 h for the coprecipitation and sol-gel samples respectively. An intermediate YAlO₃ phase was formed at 900 °C in all powders regardless of the synthesis methods. The powder morphologies obtained from TEM revealed very similar particle sizes for the two routes (20–30 nm); whilst the extent of agglomeration was higher for the sol-gel method. It was also observed that by controlling the pH in a narrow range, maintaining the precipitate processing temperature and dehydrating excess OH- ions in the precipitates using n-butanol treatment, the extent of agglomeration was further reduced in the co-precipitated nYAG powder.     

Photoluminescence emission in zirconium-doped calcium copper titanate powders

Intense photoluminescence (PL) emission was observed in Zr-doped calcium copper titanate powders. The compounds were synthesized by a soft chemical method and heat treated at temperatures between 300 and 850 °C. The decomposition of the precursors was examined by X-ray diffraction, Fourier transform infrared, Fourier transform Raman, and ultraviolet–visible spectroscopies; as well as PL analysis. Here, we discuss the role of the structural ordering, which facilitates the self-trapping of electrons and charge transfer, and review the mechanism that triggers the PL. The most intense PL emission was obtained for the sample with 5% Zr calcined at 750 °C, which is neither highly disordered nor completely ordered at ~520 nm.     

Silica coated ferrite nanoparticles: Influence of citrate functionalization procedure on final particle morphology

In this paper, magnetic nanoparticles (Fe₃O₄ and NiFe₂O₄) were coated with a biocompatible silica shell via hydrolysis and condensation of tetraethyl orthosilicate (TEOS) by the Stöber process. Magnetic nanoparticles, prepared by chemical co-precipitation from iron and nickel salts, were functionalized with citric acid, in order to provide their deagglomeration and to enable their coating with silica. The parameters of the functionalization procedure were varied (concentration–pH and type of treatment), in order to examine if and how this particular step of preparation affects the final morphology of the core-shell particles. Transmission electron microscopy, zeta potential and particle size measurements revealed that the morphology and the size of obtained core shell particles depend significantly on the core particle size, and thus on the parameters of the functionalization step.     

Synthesis of LaAlO3 powder using triethanolamine

LaAlO₃ powders were successfully synthesized by pyrolysis of complex compounds of lanthanum and aluminum with triethanolamine (TEA). The precursors and the derived powders were characterized by simultaneous thermogravimetry analysis (TG) and differential scanning calorimetry analysis (DSC), X-ray diffractometry (XRD), specific surface area measurements, and transmission electron microscopy (TEM). Pure LaAlO₃ phase was obtained at 775 °C for 2 h or 750 °C for 4 h, without formation of any intermediate phase. Pores were found from TEM images of LaAlO₃ powders prepared at 800 °C for 2 h.     

Hydrothermal synthesis of carbonate-free submicron-sized barium titanate from an amorphous precursor: Synthesis and characterization

In this paper, the amorphous barium titanate precursor was prepared by the peroxo-hydroxide method and post-treated by various drying procedures, such as: room temperature drying, room temperature vacuum drying and vacuum drying at 50 °C. The objective in the latter two treatments was to increase the Ti-O-Ba bonds of the precursor. The post-treated precursors were compared with the untreated (i.e., ‘wet’) precursor. Also, a barium titanate precursor was prepared by an alkoxide route. Afterwards, the precursors were hydrothermally treated at 200 °C in a 10 M NaOH solution. Vacuum drying of the precursor seemingly promoted the formation of Ti-O-Ti bonds in the hydrothermal end-product. The low Ba:Ti ratio (0.66) of the alkoxide-route prepared precursor lead to a multi-phase hydrothermal product with BaTiO₃ as the main phase. In contrast, phase pure BaTiO₃, i.e. without BaCO₃ contamination, was obtained for the precursor which was dried at room temperature. Cube-shaped and highly crystalline BaTiO₃ particles were observed by electron microscopy for the hydrothermally treated peroxo-hydroxide-route prepared precursor.     

Facile size-controlled synthesis of well-dispersed spherical amorphous alumina nanoparticles via homogeneous precipitation

Well-dispersed spherical amorphous alumina nanoparticles with a narrow size distribution were obtained by facile homogeneous precipitation and subsequent calcination. In the synthesis, formamide was used as the precipitant, and mixtures of aluminum sulfate and aluminum nitrate with different molar ratios were used as the aluminum sources. The average size of the amorphous alumina nanoparticles was successfully controlled by adjusting the amount of formamide and the sulfate/nitrate molar ratio. The particle size decreased with increasing amount of formamide and decreasing sulfate/nitrate molar ratio. Dispersed spherical amorphous alumina nanoparticles with average sizes of 23, 34, 45, and 57 nm were prepared using 100 mL formamide at sulfate/nitrate molar ratios of 1:9, 2:8, 3:7, and 4:6, respectively.     

Preparation of nanosized barium zirconate powder by thermal decomposition of urea in an aqueous solution containing barium and zirconium, and by calcination of the precipitate

The synthesis of barium zirconate was initiated by urea induced homogeneous precipitation followed by a “low temperature” thermal treatment. The kinetic of the reaction and the optimum urea/cation ratio have been determined by means of X-ray diffraction and Inductive Coupled Plasma analyses. It has been demonstrated that an amorphous zirconium hydrated oxide starts to precipitate followed by the precipitation of barium carbonate. A calcination at 1200 °C during 2 h gives rise to the formation of a pure barium zirconate phase. Microstructural characterisations have been performed in order to evaluate the sintering behaviour. Dilatometric measurements, coupled with scanning electron microscopy analyses clearly indicate that barium carbonate decomposition process leads to the formation of internal porosity which severely limits the density of the material, even if a sintering was performed at 1500 °C. A careful control of the heating profile seems to be necessary in order to produce dense materials.     

Glycothermal process for barium magnesium tantalate nanopowders synthesis

Barium magnesium tantalate Ba(Mg_1/3Ta_2/3)O₃ (BMT) nanopowders were synthesized at a low temperature of 220 °C through glycothermal reaction by using Ba(OH)₂·8H₂O, Mg(NO₃)·6H₂O, and TaCl₅ as precursors and 1,4-butanediol as solvent. It is demonstrated that higher synthesis temperatures and co-precipitation of magnesium and tantalum improve the incorporation of magnesium into BMT nanopowders under glycothermal treatment and produce a homogeneous, stoichiometric powder. The glycothermally derived BMT nanopowders are very reactive and provide a high-density sintered body with 97.1% of theoretical density at a low temperature of 1350 °C. The average grain size of the sintered ceramics was 1.2 ± 0.2 μm and relatively uniform in comparison with the ceramics sintered with powders produced from the conventional method.     

Fabrication and properties of CaZr0.9In0.1O3−δ prepared by an auto-ignition combustion process

One of the major challenges in developing proton conducting CaZr_0.9In_0.1O_3−δ is to achieve a high densification at low sintering temperature. In this work, an auto-ignition combustion process was first used to synthesize CaZr_0.9In_0.1O_3−δ powders aiming to improve its sinterability. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and dilatometry measurement. The results indicate that a calcination temperature of 1000 °C is sufficient to form the CaZr_0.9In_0.1O_3−δ phase. The as-obtained powders are fine, homogeneous and well crystallized, which strongly improves the sintering properties. Dense CaZr_0.9In_0.1O_3−δ ceramics with uniform grain size were obtained by sintering at 1350 °C, which is much lower than that required for the conventional solid state reaction method. In addition, the electrical properties of CaZr_0.9In_0.1O_3−δ ceramics were studied by electrochemical impedance spectroscopy.     

One-pot hydrothermal synthesis of MoS2 nanosheets/C hybrid microspheres

Uniform MoS₂ nanosheets/C hybrid microspheres with mean diameter of 320 nm have been successfully synthesized via a facile one-pot hydrothermal route by sodium molybdate reacting with sulfocarbamide in d-glucose solutions. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). XRD patterns showed that the MoS₂ was kept as a two-dimensional nanosheet crystal and C was retained as amorphous even after their annealing treatment at 800 °C. TEM and SEM images indicated that the MoS₂ nanosheets were uniformly dispersed in the amorphous carbon. The experiment results also revealed that the appropriate amount of d-glucose had an obvious effect on the formation of uniform MoS₂ nanosheets/C hybrid microspheres. A possible formation process of MoS₂ nanosheets/C hybrid microspheres was preliminarily presented.     

Hydrothermal synthesis of hierarchical hydroxyapatite: Preparation, growth mechanism and drug release property

Hydroxyapatite (HAP) hierarchical microspheres were synthesized by a facile hydrothermal method using calcium nitrate and ammonium dihydrogen phosphate through controlling complexing agents. The influences of two kinds of complexing agents (potassium sodium tartrate tetrahydrate and trisodium citrate) and reaction time on the morphology of HAP crystals have been investigated. These results indicate that complexing agents have a great influence on the morphology of HAP. When potassium sodium tartrate tetrahydrate was used as complexing agent, HAP flowers were composed of the network of nanosheet building blocks. Well-crystallized HAP dandelions with nanorods radiating from the center can be obtained by the introduction of trisodium citrate. Broader XRD diffraction peaks imply a nanometer scale size. Based on XRD and SEM results, the formation mechanism of HAP crystals has been discussed. The hierarchically structured HAP microspheres were explored as drug carriers. The results indicate that HAP flowers and dandelions showed a favorable sustained release property for ibuprofen; thus, they are very promising for application in drug delivery.     

Nanocrystalline BaAl2O4 powders prepared by aqueous combustion synthesis

In order to achieve BaAl₂O₄ formation via combustion synthesis, two types of recipes were designed: single fuel recipes (urea, glycine, β-alanine or hexamethylenetetramine) and innovative fuel mixture recipes (urea+glycine, urea+β-alanine and urea+hexamethylenetetramine respectively). No combustion reactions were noticed in the case of single fuel recipes based on urea or hexamethylenetetramine. The only crystalline phase present in the case of the powders obtained in such a way was unreacted Ba(NO₃)₂. Glycine and β-alanine generated smoldering reactions, leading to the formation of black powders, which consist of Ba(NO₃)₂, BaCO₃ and traces of BaAl₂O₄ (in the case of β-alanine). Fuel mixture recipes proved to be better than single fuel recipes, yielding BaAl₂O₄ as main crystalline phase. The specific surface area of the resulted powders ranges between 2.0 and 3.9 m²/g. The urea and glycine fuel mixture was the most efficient yielding BaAl₂O₄ with an average crystallite size of 60 nm.     

Synthesis of spherical shape borate-based bioactive glass powders prepared by ultrasonic spray pyrolysis

Spherical shape borate-based bioactive glass powders with fine size were directly prepared by high temperature spray pyrolysis. The powders prepared at temperatures between 1200 and 1400 °C had mixed phase with small amounts of fine crystal and an amorphous rich phase. Glass powders with amorphous phase were prepared at a temperature of 1500 °C. The mean size of the glass powders prepared by spray pyrolysis was 0.76 μm. The glass powders prepared at a temperature of 1200 °C had two distinct exothermic peaks (T_c1 and T_c2) at temperatures of 588 and 695 °C indicating crystallization. The glass transition temperature (T_g) of the powders prepared at a temperature of 1200 °C was 480 °C. Phase-separated crystalline phases with spherical shape were observed from the surface of the pellet sintered at a temperature of 550 °C. Crystallization of the pellet was completely occurred at temperatures of 750 and 800 °C. The pellets sintered at temperatures below 700 °C had single crystalline phase of CaNa₃B₅O₁₀. The pellet sintered at a temperature of 800 °C had two crystalline phases of CaNa₃B₅O₁₀ and CaB₂O₄.     

Polymer-assisted freeze-drying synthesis of Ag-doped ZnO nanoparticles with enhanced photocatalytic activity

Ag-doped ZnO nanoparticles with high and stable photocatalytic activity were prepared by polymer-assisted freeze-drying method with simple process and without organic solvents used. The structural morphology and optical properties of Ag-doped ZnO nanoparticles were characterized by X-ray Diffraction (XRD), Inductive Coupled Plasma Optical Emission Spectrometry (ICP-OES), Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM) and high resolution TEM (HRTEM) with energy dispersive X-ray spectroscopy, Ultraviolet-visible Diffuse Reflectance Spectroscopy (UV–vis DRS), X-ray Photoelectron Spectroscopy (XPS) and Fourier Transmission Infrared Spectroscopy (FTIR). Moreover, the thermoanalytical measurements (TGA–DTG) analysis is carried out for proper calcination temperature. XRD results show that Ag nanoparticles were successfully doped into ZnO lattice, and UV–vis DRS results indicate that the doped Ag nanoparticles result in ZnO exhibiting enhanced light trapping capability in the 400?nm and 600?nm range. The photocatalytic activity of Ag-doped ZnO was examined by analyzing the degradation of methyl orange (MO) and methylene blue (MB) dyes under UV light and solar light irradiation, and the results show that all Ag-doped ZnO nanoparticles exhibit better photocatalytic activity than those of pure ZnO nanoparticles at the same degradation conditions; especially the synthesized Ag-ZnO nanoparticles are easy to be recycled and have high photocatalytic stability. Based on the experimental results, the photocatalytic electron transfer path and the photocatalytic mechanism of Ag-ZnO nanoparticles under UV and solar irradiation conditions are explained and clarified.     

Highly efficient green synthesis of highly pure microporous nanosilica from silicomanganese slag

Highly pure nanosilica was synthesized through a facile hydrometallurgy-based method from silicomanganese slag as a low cost silica source. The synthesis route included short-term nitric acid dissolution at room temperature, gelation, washing, drying, and calcination steps. The experimental dissolution conditions resulted in a dissolution efficiency of 98%. The crystalline structure, chemical composition, chemical bonding, microstructure and elemental analyses, particle size distribution, and surface area of the extracted silica were then studied by appropriate characterization techniques. The characterization findings indicated that the amorphous silica particles had a microporous nature with an average particle size of ~24 nm, exhibiting a high purity of more than 99% and a high specific surface area of ~474 m² g^?1. The overall results indicated that the proposed synthesis route is a promising feasible alternative method to produce highly pure microporous nanosilica from a low cost secondary resource. The proposed method can treat 98% of the slag and uses less chemicals than conventional methods and is therefore a greener nanosilica production process. The current process also competes with the traditional process and other recently introduced processes in terms of process economy and the quality of the produced product.