Preparation of cube micrometer potassium niobate (KNbO3) by hydrothermal method and sonocatalytic degradation of organic dye

Cube micrometer potassium niobate (KNbO₃) powder, as a high effective sonocatalyst, was prepared using hydrothermal method, and then, was characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). In order to evaluate the sonocatalytic activity of prepared KNbO₃ powder, the sonocatalytic degradation of some organic dyes was studied. In addition, some influencing factors such as heat-treatment temperature and heat-treatment time on the sonocatalytic activity of prepared KNbO₃ powder and catalyst added amount and ultrasonic irradiation time on the sonocatalytic degradation efficiency were examined by using UV–visible spectrophotometer and Total Organic Carbon (TOC) determination. The experimental results showed that the best sonocatalytic degradation ratio (69.23%) of organic dyes could be obtained when the conditions of 5.00 mg/L initial concentration, 1.00 g/L prepared KNbO₃ powder (heat-treated at 400 °C for 60 min) added amount, 5.00 h ultrasonic irradiation (40 kHz frequency and 300 W output power), 100 mL total volume and 25–28 °C temperature were adopted. Therefore, the micrometer KNbO₃ powder could be considered as an effective sonocatalyst for treating non- or low-transparent organic wastewaters.     

Landau-type pressure dependence of the order parameter: application to the ferroelectric-paraelectric pressure-induced transition in KNbO3

Following the Landau model, the pressure–temperature dependence of the order parameter is derived. Using the Lyddane–Sachs–Teller (LST) relationship, the model is applied to ferroelectricity to deduce the pressure behaviour of the soft mode driving the transition. Comparison with experiment is made using recent data obtained on KNbO₃ under pressure over a large temperature range. The results indicate that the ferroelectric–paraelectric (FE–PE) transition observed in KNbO₃ at high pressure from ～4 to ～25?GPa is of the second-order type.     

Quantum chemical modelling of ‘green’ luminescence in self activated perovskite-type oxides

We discuss the origin of the intrinsic visible band emission of ABO₃ perovskite oxides (so-called ‘green luminescence’) which remains a topic of high interest during the last quarter of the century. We present a theoretical calculation modelling of this emission in the framework of a concept of charge transfer vibronic excitons [Phys. Solid State, 40 (1998) 834], i.e. as a result of radiative recombination of correlated (bound) self-trapped electron and hole polarons in the highly polarizable ABO₃-type matrix. The Intermediate Neglect of Differential Overlap method combined with the Large Unit Cell periodic defect model was used for quantum chemical calculations and theoretical simulation of the green emission for a series of model ABO₃ perovskites. The ‘green’ luminescence energies for PbTiO₃, SrTiO₃, BaTiO₃, KNbO₃ and KTaO₃ perovskite-type crystals agree well with those experimentally observed earlier.     

Modelling of the phase transitions sequence in KNbO3 and BaTiO3

Interatomic potentials are determined in the framework of the nonlinear oxygen polarizability model to describe the structural behavior of KNbO₃ and BaTiO₃ as a function of temperature. To this purpose, the adiabatic potential is evaluated for different ferroelectric distortions and the model potential parameters are improved by comparing with total energies from full-potential LMTO calculations. Phonon dispersion curves are computed to test if the model reproduces the pronounced two-dimensional character instabilities found by first-principles lattice dynamics using a linear response approach. Finally, the phase diagram for KNbO₃ is obtained through a constant-pressure molecular dynamics simulation.     

Investigation of the phase transitions of ferroelectric KIO3 and KNbO3 crystals by optical diffraction

Optical diffraction is reviewed as a technique for investigation of the phase transitions in crystals with a multidomain structure. It has been used to study the phase transitions in KIO₃ and KNbO₃ single crystals. Strong optical diffraction bands resulted from electric domains in KNbO₃ crystals and their change with temperature were observed when a laser beam passed through the crystals. The diffraction patterns observed changed abruptly at 427°C, 223°C, and -50°C respectively, at which KNbO₃ crystals undergo structural phase transitions. It is considered that the change of the diffraction patterns with temperature is due to change of the electric domains in the crystals.     

Photoconductivity and light-induced absorption in KNbO3:Fe

Measurements of photoconductivity and light-induced absorption in KNbO₃: Fe are performed at different light intensities and crystal temperatures. The results are interpreted in terms of a two-center charge transport model. Different model parameters may be evaluated from the experimental data. A complete set of parameters is suggested explaining the dependences of photoconductivity and light-induced absorption on light intensity and temperature for the KNbO₃: Fe crystal investigated.     

Diffraction efficiency and energy transfer during hologram formation in reduced KNbO3

Volume phase-hologram formation by the photorefractive effect in KNbO₃ is accompanied by a stationary energy transfer between writing beams. The change in energy transfer by applying an electric field on the reduced crystals is shown to be due to an efficient increase in migration length which can reach values comparable or larger than the fringe spacing. It is demonstrated that photovoltaic contribution to the diffraction efficiency and energy transfer is rather small in reduced KNbO₃ and that diffusion of photogenerated free holes is the dominant charge transport for the photorefractive effect in unbiased crystals. The experimental results for diffraction efficiency and energy transfer as a function of grating spacing, electric field, light intensity and temperature is well described by a recent theory of Kukhtarev and Vinetskii.     

Structure and lattice dynamics of solid solutions (1 − x)BiFeO3-xANbO3 (A = K,Na)

The structures and the dynamic characteristics of the lattices of two compositions of solid solutions of multiferroic BiFeO₃ with ferroelectric KNbO₃ and antiferroelctric NaNbO₃, namely, (1 ? x)BiFeO₃-xKNbO₃ and (1 ? x)BiFeO₃-xNaNbO₃, have been studied using X-ray powder diffraction and Raman spectroscopy. For these systems with x = 0.3, 0.5, and 0.7, the symmetry and unit cell parameters at room temperature have been determined. An analysis of the vibrational spectra has revealed sequences of rotational distortions with variations in the concentrations of components.     

Hydrothermal Synthesis of Metal Oxide Nanoparticles at Supercritical Conditions

Hydrothermal synthesis of CeO₂ and AlO(OH) were conducted using a flow type apparatus over the range of temperature from 523 to 673 K at 30 MPa. Nanosize crystals were formed at supercritical conditions. The mechanism of nanoparticle formation at supercritical conditions was discussed based on the metal oxide solubility and kinetics of the hydrothermal synthesis reaction. The reaction rate of Ce(NO₃)₃ and Al(NO₃)₃ was evaluated using a flow type reactor. The Arrhenius plot of the first order rate constant fell on a straight line in the subcritical region, while it deviated from the straight line to the higher values above the critical point. The solubility of Ce(OH)₃ and AlO(OH) was estimated by using a modified HKF model in a wide range of pH and temperature. In acidic conditions, where hydrothermal synthesis reaction is concerned, solubility gradually decreased with increasing temperature and then drastically dropped above the critical point. The trend of the solubility and the kinetics around the critical point could be explained by taking account of the dielectric constant effect on the reactions. There are two reasons why nanoparticle are formed at supercritical conditions. Larger particles are produced at subcritical conditions due to Ostwald ripening; that could not be observed in supercritical water because of the extremely low solubility. Second reason is the faster nucleation rate in supercritical water because of the lower solubility and the extremely fast reaction rate.     

Effect of low-temperature high-pressure sintering on BiFeO3 density,electrical magnetic and structural properties

Single-phase multiferroic BiFeO₃ (BFO) powders were prepared by hydrothermal microwave synthesis and dense BiFeO₃ ceramics were fabricated for the first time by the low-temperature high-pressure (LTHP) sintering technique. Effect of sintering temperature ranging from 400 to 800 °C (3 min and 10 min) and pressure of 3–8 GPa on structural, microstructural, electric and magnetic properties were investigated through X-ray diffraction, scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), density and magnetic measurements. The results highlighted that LTHP sintering method, thanks to the high pressure involved, requires lower temperature and shorter time than other techniques, avoiding BiFeO₃ phase degradation. SEM images show that for short experimental time (t = 3 min) the average grain size of the sintered samples was approximately the same size of raw powder. Extending the sintering time up to 10 min the grain growth phenomena occurred. Moreover the results indicate that the best obtained density value was around 98% of theoretical density. The dielectric behavior of BiFeO₃ ceramics was not significantly influenced by the LTHP sintering conditions. Magnetic measurements showed that ceramic BiFeO₃ is weakly ferromagnetic at room temperature.     

Nucleation of domains under the influence of temperature in Ba5Ti2O7Cl4

It is found that the nucleation of domains can take place in Ba₅Ti₂O₇Cl₄ under the influence of temperature unlike in many other ferroelectrics. The nucleated domain can also be removed from the structure under the randomizing effect of temperature. These observations have been explained on the basis of a nucleation model of Ingle and coworkers suggested for KNbO₃. Similarity of physical situation in KNbO₃ and Ba₅Ti₂O₇Cl₄ regarding the existence of ordered point defects inducing nucleation of domains around them has been highlighted. This surprising similarity is suggested to be due to the physical processes occurring at the phase transition rather than due to any structural resemblance. The nature of nucleation occurring under the influence of temperature is shown to be identical with the nature of nucleation occurring under the influence of externally applied stress, and/or DC electric field. A new technique of identifying point defects responsible for nucleation of domains is reported.     

铁电超晶格的一个唯象模型

引入了一个描述铁电超晶格行为模式的唯象模型.在模型中,同时考虑体与体之间的多种耦合方式.通过数值模拟,得出了超晶格的极化强度、居里温度、临界尺寸和耦合系数之间的关系.认为耦合参数c是一个与温度、晶格尺寸相关的函数,进而提出了一个关于耦合参数c的经验公式,解释了一个近期的关于KTaO₃/KNbO₃超晶格材料的实验结果. 关键词：     

A new approach to the drug release kinetics of a discrete system: SiO2 system obtained by ultrasonic dry spraying

Mesoporous silica materials have already proved to be non-toxic and biocompatible, and also to have large pore volume and very high specific surface area suitable for loading of small molecules. Having this in mind and the fact that silicon dioxide (SiO₂) powders can be so designed to obtain particle structures organized at multi levels, SiO₂ was chosen as a potential carrier for metronidazole, an antibiotic drug. SiO₂ powder was synthesized in two stages: first silica sol was prepared by hydrothermal synthesis and second the sol was converted into powder by dry spraying with simultaneous incorporation of the antibiotic into its structure. Scanning and transmission electron microscopy study revealed very complex structure and sub-structure of SiO₂ particles. Cell viability tests were used for estimation of cytotoxicity of so synthesized SiO₂. The drug release data showed that the system can provide drug release for a long time. Also, the device behavior is fully predictable, according to our theoretical model of multilevel structure design, and gives many opportunities for model investigations of drug release and its kinetics. The pore sizes and their distribution were observed as a limiting factor of drug release kinetics. Therefore, as the pore sizes are given as a set of discrete values, the kinetics of drug release might also be given as a set of corresponding discrete values.     

Synthesis and optical properties of tetragonal KTa0.6Nb0.4O3 nanoparticles

Tetragonal phase KTa_0.6Nb_0.4O₃ (KTN) nanoparticles have been prepared by hydrothermal method. The obtained particles were characterized by X-ray powder diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy and UV-vis absorption spectrum techniques. A systematic change in crystal structure from cubic to tetragonal is observed with the increase of reaction temperature and KOH concentration. Room temperature UV-vis absorption spectrums of KTN particles show that the band gap changes from 3.24 to 3.34 eV with grain size diminished, which reveals the existence of blue-shift phenomenon of absorption bands.     

Brownian relaxation of magnetic nanoparticles in fluid: the effect of the solvent

A simple, environmentally friendly hydrothermal stripping route for synthesizing highly size-controlled spherical ferric oxide nanoparticles was developed that involved stripping ferric ion from iron-loaded organic phase. The particle size was found to be influenced by the initial concentration of iron in organic phase, stripping temperature and time, and a mathematical model about the size was established based on the experimental results and theoretical analysis. The model suggests that the process apparent activation energy of stripping iron from organic phase is 97.3? kJ·mol^?1, the energy of crystal growth is 51.6? kJ·mol^?1, and the synthesis of Fe₂O₃ is controlled by the crystal growth of embryo at low temperature (T < 590?K). The sizes calculated by the model comparatively accord with the experimental data and this provides a method for controlling the sizes.     

Synthesis of nanocrystalline magnesium nitride (Mg3N2) powder using thermal plasma

Nanocrystalline magnesium nitride (Mg₃N₂) powder was synthesized from bulk magnesium by thermal plasma at atmospheric pressure. Magnesium vapor was generated through heating the bulk magnesium by DC plasma jet and reacted with ammonia gas. Injecting position and flow rates of ammonia gas were controlled to investigate an ideal condition for Mg₃N₂ synthesis. The synthesized Mg₃N₂ was cooled and collected on the chamber wall. Characteristics of the synthesized powders for each experimental condition were analyzed by X-ray diffractometer (XRD), scanning electron microscopy (SEM) and thermogravity analysis (TGA). In absence of NH₃, magnesium metal powder was formed. The synthesis with NH₃ injection in low temperature region resulted in a formation of crystalline magnesium nitride with trigonal morphology, whereas the mixture of magnesium metal and amorphous Mg₃N₂ was formed when NH₃ was injected in high temperature region. Also, vaporization process of magnesium was discussed.     

Extended X-ray absorption fine-structure (EXAFS) of a complex oxide structure: a full multiple scattering analysis of the Au L3-edge EXAFS of Au2O3

Crystalline Au₂O₃ was obtained by hydrothermal synthesis at 3000 atm and its extended X-ray absorption fine-structure (EXAFS) at the Au L₃-edge was measured at room temperature. A detailed full multiple scattering (MS) analysis using FEFF8 theory shows that only a small number of scattering paths contribute significantly to the EXAFS of Au₂O₃. Because of the complex unit cell (low local symmetry) of the Au₂O₃ structure, contributions of MS paths are almost negligible. The results indicate that FEFF8 theory provides a good reference for the analysis of Au-O phases.     

Template growth of vertically aligned carbon nanotubes using self-assembled monolayers of SiO2 particles by Langmuir–Blodgett technique

The thermal stability of nanocrystalline 3R-CuCrO₂ obtaining by hydrothermal method was investigated by annealing treatment, XRD, FT-IR, XPS and TG. The three temperature domains corresponding to thermal stability of 3R-CuCrO₂ nanocrystals (25–400 °C), destabilization of nanocrystalline 3R-CuCrO₂ phase (400–800 °C) and recrystallization of 3R-CuCrO₂ in microcrystalline state over 800 °C, were determined by the specific hydrothermal synthesis conditions. This study has indicated that nanocrystals with delafossite structure synthesized by hydrothermal method exhibit nanocrystalline state up to a reasonably high temperature, about 390 °C, which could be interesting for technical applications and the classical theory of the grain growth.     

Investigation of specific features of the lattice dynamics and the ferroelectric transition in perovskite crystals

The specific features of diffuse X-ray scattering in BaTiO₃, KNbO₃, and PbTiP₃ perovskite crystals have been investigated. The former two perovskite compounds in cubic, tetragonal, and orthorhombic phases exhibit anomalous sheets due to diffuse X-ray scattering, whereas no similar sheets are observed in the case of diffuse X-ray scattering in PbTiO₃. For these compounds, the phonon spectra are calculated in the quasi-harmonic approximation within the polarizable-shell model, and the mechanism of stabilization of the soft mode above the temperature of the phase transition to the ferroelectric state is considered. It is demonstrated that, in the cubic phase of BaTiO₃ and KNbO₃ crystals, there exist quasi-one-dimensional “soft” modes of vibrations of ions in M-O-M-O- chains, where M = Ti or Nb. In PbTiO₃, this feature of the soft mode has not been revealed. The pair correlation functions of simultaneous atomic displacements in BaTiO₃, KNbO₃, and PbTiO₃ are determined and used to calculate the intensity of diffuse X-ray scattering. The results obtained are in good agreement with experimental data. This is a strong argument in support of the hypothesis that the specific features of diffuse scattering are associated with the existence of quasi-one-dimensional correlations of atomic displacements in the soft optical mode and that the ferroelectric transition in perovskites is a displacive ferroelectric phase transition. The possible influence of the specific features revealed in the phonon spectra of the perovskite crystals on the processes of nuclear magnetic resonance and X-ray absorption (extended X-ray absorption fine structure spectra) is briefly discussed.     

Desorption of carbon dioxide from small potassium niobate particles induced by the particles’ ferroelectric transition

The aim of this work is to understand surface properties of ferroelectric crystals related to gas adsorption. Various ferroelectric crystals involved in these studies readily adsorb carbon dioxide, thus our studies were centered on adsorption studies of this molecule. It has been claimed that a dipole moment is induced on carbon dioxide molecules that are near an oxide surface. Our experiments explored the possibility of a dipole-dipole interaction between the gas molecule and the ferroelectric oxide surface in order to explain its adsorption. We characterized the samples with scanning electron microscopy, X-ray diffraction and Raman spectroscopy. We determined the ferroelectric nature of the particles and studied the temperature-dependent phase transitions in small particles of KNbO₃ using Raman spectroscopy. We were able to correlate desorption of CO₂ from one surface state of KNbO₃ with the occurrence of the orthorhombic to tetragonal transition in KNbO₃ in particles of 1 μm size. This CO₂ surface site was not observed in KTaO₃, which does not show ferroelectricity at room temperature.