Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.     

Surface sprouting growth of Na2Nb2O6·H2O nanowires and fabrication of NaNbO3 nanostructures with controlled morphologies

The one-dimensional (1D) Sandia octahedral molecular sieves (SOMS) Na₂Nb₂O₆·H₂O nanowires were prepared by the reaction of Nb powder with NaOH via a one-step hydrothermal methods. The products were characterized by SEM, TEM, XRD, IR and EDX. A plausible sprouting growth mechanism is proposed for the formation of Na₂Nb₂O₆·H₂O nanowires based on the systematic investigation. Na₂Nb₂O₆·H₂O nanoribbons-based complex flowerlike structure were first grew on the metallic niobium surface, the growth process of SOMS nanowire is similar to the plant seed sprouting and growing, Na₂Nb₂O₆·H₂O nanowires were finally formed at the depletion of metallic niobium powder. In the end, we showed that Na₂Nb₂O₆·H₂O nanowires is hydrothermally synthesized in the 15 M NaOH solution at 423 K, which can be easily converted into NaNbO₃ nanowires by calcination, while the NaNbO₃ cubes were obtained through the same hydrothermal process at a higher temperature of 453 K.     

Synthesis,photophysical properties,and photocatalytic applications of Bi doped NaTaO3 and Bi doped Na2Ta2O6 nanoparticles

Phase formation and photophysical properties of bismuth doped sodium tantalum oxide (perovskite, defect pyrochlore) nanoparticles prepared by a hydrothermal method were studied in detail. It was revealed that the synthesis conditions like NaOH concentration and bismuth precursor (NaBiO₃·2H₂O) markedly affect the crystal structure of sodium tantalum oxide. At low NaOH concentration and high bismuth precursor (NaBiO₃·2H₂O) content, Bi doped Na₂Ta₂O₆ (defect pyrochlore) phase was predominantly formed, while at higher NaOH concentration, Bi doped NaTaO₃ (perovskite) phase was formed. It was observed that the defect pyrochlore (Bi doped Na₂Ta₂O₆) phase was formed and stabilized by the presence of dopant precursor (NaBiO₃·2H₂O). The chemical analysis of the samples confirmed the doping of Bi³⁺ cations in both phases. Doping of bismuth enabled visible light absorption up to 500 nm in perovskite and defect pyrochlore type sodium tantalum oxide. Bi doped NaTaO₃ samples showed better performance for the photocatalytic degradation of rhodamine B than that of Bi doped Na₂Ta₂O₆, under visible light irritation (λ>420 nm). The present results shed light on phase formation of sodium tantalate and these results are useful in understanding properties of NaTaO₃ based compounds, synthesized by the hydrothermal method.     

Synthesis of Fe3O4 nanoparticles without inert gas protection used as precursors of magnetic fluids

Fe₃O₄ nanoparticles were hydrothermally synthesized under continuous microwave irradiation from FeCl₃·6H₂O and FeSO₄·7H₂O aqueous solutions, using NH₄OH as precipitating reagent and N₂H₄·H₂O as oxidation-resistant reagent. The results of X-ray powder diffraction (XRD), FT–IR spectroscopy and scanning electron microscopy (SEM) measurements showed that the synthesized magnetite (Fe₃O₄) nanoparticles had an average diameter of 10 nm. The magnetic properties of the Fe₃O₄ nanoparticles were measured using a vibrating sample magnetometer (VSM), indicating that the nanoparticles possessed high saturation magnetization at room temperature. The Fe₃O₄ nanoparticles were used to prepare magnetic fluids (MFs) based on water, and the properties of the MFs were characterized by a Gouy magnetic balance, a capillary rheometer and a rotating rheometer, respectively.     

Nanocrystalline oxide (Y2O3, Dy2O3, ZrO2, NiO) coatings on BaTiO3 submicron particles by precipitation

Nanocoatings (5–20 nm) of different compounds on fine BaTiO₃ particles were obtained by means of precipitation processes. Homogeneous and smooth shells of Y(OH)CO₃ and Dy(OH)CO₃ were grown from nitrate solutions in the presence of urea. An irregular coating consisting of zirconia nanoparticles was produced from zirconyl nitrate solution using ammonia as a precipitating agent after adsorption of a polymeric polyelectrolyte on the BaTiO₃ surface. Composite particles with a peculiar morphology were obtained by inducing heterogeneous nucleation and growth of Ni(OH)₂ lamellae on the BaTiO₃ surface. The different shells can be transformed in a nanocrystalline coating of the corresponding oxide (Y₂O₃, Dy₂O₃, ZrO₂, NiO) by calcination at moderate temperatures (400–700 °C). The overall results indicate that precipitation from solution represents a versatile process to grow a second-phase layer on the surface of BaTiO₃ particles. This approach can be used as an alternative to mechanical wet mixing for controlled doping of ferroelectric materials and for the fabrication of composite materials with specific geometry of the two-phase assembly.     

Enhanced ferroelectric properties of (Pb0.90La0.10)Ti0.975O3 multilayered thin films prepared by RF magnetron sputtering

The (Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PLT/PT), PbTiO₃/(Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PT/PLT/PT) multilayered thin films with a PbO_x buffer layer were in situ deposited by RF magnetron sputtering at the substrate temperature of 600 °C. With this method, highly (1 0 0)-oriented PLT/PT and PT/PLT/PT multilayered thin films were obtained. The PbO_x buffer layer leads to the (1 0 0) orientation of the films. The dielectric, ferroelectric and pyroelectric properties of the PLT multilayered thin films were investigated. It is found that highly (1 0 0)-oriented PT/PLT/PT multilayered thin films possess higher remnant polarization 2P_r (44.1 μC/cm²) and better pyroelectric coefficient at room temperature p (p = 2.425 × 10⁻⁸ C/cm² K) than these of PLT and PLT/PT thin films. These results indicate that the design of the PT/PLT/PT multilayered thin films with a PbO_x buffer layer should be an effective way to enhance the dielectric, ferroelectric and pyroelectric properties. The mechanism of the enhanced ferroelectric properties was also discussed.     

Surface characterization of the Zn-Ni-Al2O3 nanocomposite coating fabricated under ultrasound condition

Zn-Ni-Al₂O₃ nanocomposite coating, which was fabricated by eletrodeposition technique with the aid of ultrasound, was investigated by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis and X-ray photoelectron spectroscopy (XPS). The results reveal that 7.2 wt.% nano-alumina particles uniformly dispersed in the matrix of the composite coating. The XPS analyses demonstrate that the outermost layer of Zn-Ni-Al₂O₃ coating was composed of nano-alumina and Zn(OH)₂, while the transition layer between the outermost layer and the Zn-Ni matrix consisted of nano-alumina, metallic Zn, ZnO and metallic Ni. In order to investigate the influences of ultrasonic agitation and the incorporation of nano-alumina on the composition and surface structure of Zn-Ni matrix, the comparison studies of Zn-Ni-Al₂O₃ nanocomposite coating with Zn-Ni coatings fabricated with and without ultrasound were conducted. The results indicate that ultrasonic agitation resulted in a decrease of Ni content in the Zn-Ni matrix and an increase of the thickness of surface oxide layer; while the incorporation of nano-α-Al₂O₃ increased the Ni content in the Zn-Ni matrix.     

Study of phase transition in ZrO2 doped with Pb3O4

Electrical conductivity of ZrO₂ doped with Pb₃O₄ has been measured at different temperatures for different molar ratios (x=0, 0.01, 0.02, 0.03, 0.04, 0.05 and 0.06). The conductivity increases due to migration of vacancies, created by doping. The conductivity increases with increase in temperature till 180 °C and thereby decreases due to collapse of the fluorite framework. A second rise in conductivity at higher temperatures beyond 500-618 °C is due to phase transition of ZrO₂. DTA and X-ray powder diffraction were carried out for confirming doping effect and transition in ZrO₂.The addition of Pb₃O₄ to ZrO₂ shifted the phase transition of ZrO₂ due to the interaction between Pb₃O₄ and ZrO₂.     

Microwave-assisted synthesis of SrFe12O19 hexaferrites

Ultra-fine and homogeneous SrFe₁₂O₁₉ hexaferrites were synthesized by a microwave-assisted calcination route. The calcined precursors were prepared by a sol-gel auto-combustion method using Fe(NO₃)₃·9H₂O, Sr(NO₃)₂ and citric acid as starting materials. The structures, powder morphology and magnetic properties of the products were characterized by X-ray diffraction, scanning electron microscope and vibrating sample magnetometer. The results showed that microwaves are helpful to reduce the calcination temperature and shorten the calcination time. The ferrites with saturation magnetization, remanence and intrinsic coercivity of 54.80 emu/g, 29.52 emu/g and 5261 Oe, respectively, were obtained in samples calcined at 800 °C for 80 min.     

Conductivity and water uptake of Sr4(Sr2Nb2)O11·nH2O and Sr4(Sr2Ta2)O11·nH2O

The hydrated oxygen deficient complex perovskite-related materials Sr₄(Sr₂Nb₂)O₁₁·nH₂O and Sr₄(Sr₂Ta₂)O₁₁·nH₂O were studied at high water vapour pressures over a large temperature range by electrical conductivity measurements, thermogravimetry (TG), and X-ray powder diffraction (XRPD). In humid atmospheres both materials are known to exhibit protonic conductivity below dehydration temperatures, with peak-shaped maxima at about 500 °C. In this work we show that the peaks expand to plateaus of high conductivity from 500 to 700 °C at a water vapour pressure of 1 atm. However, in situ synchrotron XRPD of Sr₄(Sr₂Nb₂)O₁₁·nH₂O as a function of temperature shows that these observations are in fact coincident with melting and dehydration of a secondary phase Sr(OH)₂. The stability of Sr₄(Sr₂Nb₂)O₁₁·nH₂O and Sr₄(Sr₂Ta₂)O₁₁·nH₂O in humid atmospheres is thus insufficient, causing decomposition into perovskites with lower Sr content and SrO/Sr(OH)₂ secondary phases. This, in turn, rationalizes the observation of peaks and plateaus in the conductivity of these materials.     

Structural and electrical impedance study of Pb(Sr1/3Nb2/3)O3

Lead-based ceramic Pb(Sr_1/3Nb_2/3)O₃ (PSN) is prepared by the columbite precursor method and structurally characterized using XRD. The X-ray diffraction shows a perovskite structure with cubic pyrochlore phase. Detailed studies of ε′ and ε″ of the compounds show that the compounds exhibit dielectric anomaly. Impedance spectroscopy is used to characterize the electrical behaviour. Results indicate that the relaxation mechanism of the material is temperature dependent and has dominant bulk contribution in different temperature ranges. Modulus spectroscopic data were used to gain an insight into the electrical properties of the samples and with a view to observe the relaxations in them. Frequency dependence dielectric permittivity shows typical Debye-type dielectric dispersion. Temperature-dependent DC resistivity shows that resistance decreases with the increase in temperature and follows Arrhenius behaviour in different temperature regions.     

Concerning the cation distribution in MnFe2O4 synthesized through the thermal decomposition of oxalates

A single phase manganese ferrite powder have been synthesized through the thermal decomposition reaction of MnC₂O₄·2H₂O-FeC₂O₄·2H₂O (1:2 mole ratio) mixture in air. DTA-TG, XRD, Mössbauer spectroscopy, FT-IR and SEM techniques were used to investigate the effect of calcination temperature on the mixture. Firing of the mixture in the range 300-500 °C produce ultra-fine particles of α-Fe₂O₃ having paramagnetic properties. XRD, Mössbauer spectroscopy as well as SEM experiments showed the progressive increase in the particle size of α-Fe₂O₃ up to 500 °C. DTA study reveals an exothermic phase transition at 550 °C attributed to the formation of a Fe₂O₃-Mn₂O₃ solid solution which persists to appear up to 1000 °C. At 1100 °C, the single phase MnFe₂O₄ with a cubic structure predominated. The Mössbauer effect spectrum of the produced ferrite exhibits normal Zeeman split sextets due to Fe³⁺ions at tetrahedral (A) and octahedral (B) sites. The obtained cation distribution from Mössbauer spectroscopy is (Fe_0.92Mn_0.08)[Fe_1.08Mn_0.92]O₄.     

Preparation of Fe2O3/SrTiO3 composite powders and their photocatalytic properties

Fe₂O₃/SrTiO₃ composite powders have been prepared and their photocatalytic activities were investigated by photooxidizing methanol. These powders were characterized by ultraviolet (UV)-visible diffuse reflectance spectra, scanning electron microscope (SEM) and X-ray diffraction (XRD). The results showed that the Fe₂O₃/SrTiO₃ composite powders with optimum proportion exhibited higher photocatalytic activity than pure SrTiO₃, Fe₂O₃ and TiO₂ (P25) under visible light (λ>440 nm) irradiation. The SEM image of the composite powders showed that SrTiO₃ and Fe₂O₃ particles contacted well. Further research revealed that the calcination temperature is an important factor in the preparation of the composite powder with relatively high photocatalytic ability.     

α-Fe2O3-In2O3 mixed oxide nanoparticles synthesized under hydrothermal supercritical conditions

α-Fe₂O₃-In₂O₃ mixed oxide nanoparticles system has been synthesized by hydrothermal supercritical and postannealing route, starting with (1−x)Fe(NO₃)₃·9H₂O·xIn(NO₃)₃·5H₂O aqueous solution (x=0-1). X-ray diffraction and Mössbauer spectroscopy have been used to study the phase structure and substitutions in the nanosized samples. The concentration regions for the existence of the solid solutions in the α-Fe₂O₃-In₂O₃ nanoparticle system together with the solubility limits of In³⁺ ions in the hematite lattice and of Fe³⁺ ions in the cubic In₂O₃ structure have been evidenced. In general, the substitution level is considerably lower than the nominal concentration x. A justification of the processes leading to the formation of iron and indium phases in the investigated supercritical hydrothermal system has been given.     

A new hydrothermal blackening technology for Fe3O4 coatings of carbon steel

This paper proposes a new blackening technology for growing magnetite (Fe₃O₄) coating on surface of carbon steel. Dense black coating composed of Fe₃O₄ ultrafine particles could be successfully prepared by hydrothermal treatment of the carbon steel substrate in the N₂H₄·H₂O-FeSO₄-NaOH solution at 150 °C. Electrochemical analysis, including Tafel and electrochemical impedance spectroscopy, indicated that the anodic dissolution reaction was effectively limited and the corrosion resistance increased by the Fe₃O₄ coating. The key factors and growth mechanism for the hydrothermal formation of the Fe₃O₄ coating are also discussed.     

High pyroelectric power generation of 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 single crystal

We report the pyroelectric power generation of a relaxor ferroelectric 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃ (PMN–PT) single crystal. For a temperature variation rate of 0.5 K/s, the PMN–PT generated a closed-circuit current of 10 nA and an open-circuit voltage of 1.1 V at room temperature. The pyroelectric current and voltage of the PMN–PT single crystal were proportional to the temperature variation rate and were sharply enhanced near the structural phase-transition temperature. Additionally, the PMN–PT pyroelectric generator produced stable power for excessive thermal cycling and was highly sensitive to random thermal fluctuations. Our results indicate the potential importance of PMN–PT for high-power pyroelectric generator applications.     

Static susceptibility and heat capacity studies on V3O7·H2O7 nanobelts

V₃O₇·H₂O nanobelts were prepared by a hydrothermal method at 190 °C using V₂O₅·nH₂O gel and H₂C₂O₄·2H₂O as starting agents. The obtained nanobelts have diameters ranging from 40 to 70 nm with lengths up to several micrometers. Measurements of the static magnetic susceptibility and the specific heat show a discontinuous phase transition at around T=145 K, which separates two regions of paramagnetic behavior.     

Intralamellar structural modifications related to the proton exchanging in K4Nb6O17 layered phase

Basic structural aspects about the layered hexaniobate of K₄Nb₆O₁₇ composition and its proton-exchanged form were investigated mainly by spectroscopic techniques. Raman spectra of hydrous K₄Nb₆O₁₇ and H₂K₂Nb₆O₁₇·H₂O show significant modifications in the 950-800 cm⁻¹ region (Nb-O stretching mode of highly distorted NbO₆ octahedra). The band at 900 cm⁻¹ shifts to 940 cm⁻¹ after the replacement of K⁺ ion by proton. Raman spectra of the original materials and the related deuterated samples are similar suggesting that no isotopic effect occurs. Major modifications were observed when H₂K₂Nb₆O₁₇ was dehydrated: the relative intensity of the band at 940 cm⁻¹ decreases and new bands seems to be present at about 860-890 cm⁻¹. The H⁺ ions should be shielded by the hydration sphere what preclude the interaction with the layers. Removing the water molecules, H⁺ ions can establish a strong interaction with oxygen atoms, decreasing the bond order of Nb-O linkage. X-ray absorption near edge structure studies performed at Nb K-edge indicate that the niobium coordination number and oxidation state remain identical after the replacement of potassium by proton. From the refinement of the fine structure, it appears that the Nb-Nb coordination shell is divided into two main contributions of about 0.33 and 0.39 nm, and interestingly the population, i.e., the number of backscattering atoms is inversed between the two hexaniobate materials.     

Synthesis and structure of the monolayer hydrate K0.3CoO2·0.4H2O

The monolayer hydrate (MLH) K_0.3CoO₂·0.4H₂O was synthesized from K_0.6CoO₂ by extracting K⁺ cations using K₂S₂O₈ as an oxidant and the subsequent intercalation of water between the layers of edge-sharing CoO₆ octahedra. A hexagonal structure (space group P6₃/mmc) with lattice parameters a=2.8262(1) Å, c=13.8269(6) Å similar to the MLH Na_0.36CoO₂·0.7H₂O was established using high-resolution synchrotron X-ray powder diffraction data. The K/H₂O layer in the K-MLH is disordered, which is in contrast to the Na-MLH. At low temperatures metallic and paramagnetic behavior was found.     

Photocatalytic activity of Nb2O5/SrNb2O6 heterojunction on the degradation of methyl orange

The pure SrNb₂O₆ powders were prepared at 1400 °C by a conventional solid-state method and characterized by X-ray powder diffraction and UV-vis diffuse reflection spectrum. The powders of Nb₂O₅ and SrNb₂O₆ were ball-milled together and annealed to form the Nb₂O₅/SrNb₂O₆ composite. Photocatalytic activities of the composites were investigated on the degradation of methyl orange. The results show that the proportion of Nb₂O₅ to SrNb₂O₆ and the annealing temperature greatly influence the photocatalytic activities of the composites. The best photocatalytic activity occurs when the weight proportion of Nb₂O₅ to SrNb₂O₆ is 30% and the annealing temperature is 600 °C. The tremendously enhanced photocatalytic activity of the Nb₂O₅/SrNb₂O₆ composite compared to Nb₂O₅ or SrNb₂O₆ is ascribed to the heterojunction effect taking place at the interface between particles of Nb₂O₅ and SrNb₂O₆. The powders also show a higher photocatalytic activity than commercial anatase TiO₂.