Sintering and electrical properties of Na0.5K0.5NbO3 ceramics modified with lanthanum and iron oxides

Effects of La³⁺, Fe³⁺ doping and their co-doping on the sintering, structures and electrical properties of Na_0.5K_0.5NbO₃ (NKN) ceramics were investigated. A significant modification of sintering behavior can be obtained by the addition of Fe₂O₃. On the contrary, the addition of La₂O₃ and La–FeO₃ tends to degrade the densification. Moreover, Fe³⁺ doping does not change the crystal structure, thus leading to an unchanged Curie temperature. Owing to a transition from orthorhombic to pseudo-cubic structures, the Curie temperatures of NKN ceramics were significantly lowered by doping La₂O₃ and La–FeO₃. NKN ceramics modified with a small amount of Fe₂O₃ and La–FeO₃ (less than 0.5 mol%) exhibit improved ferroelectric, piezoelectric and electromechanical properties.     

Temperature Raman scattering study of CaAl0.5Ta0.5O3 perovskite crystal

Temperature Raman scattering studies were performed for CaAl_0.5Ta_0.5O₃ crystal. This material features NaCl-type ordering of Al³⁺ and Ta⁵⁺ ions at the B-site superimposed onto b⁻b⁻c⁺ octahedral tilting. Because of the existing twin-related domains in crystal structure, the micro-Raman measurements were carried out at room temperature. Some differences in Raman spectra obtained using macro- and micro-Raman system were revealed. Most of the Raman modes show monotonous red-shift with the increase in temperature. Only the cubic-like fully symmetric A_1g mode slightly increases its frequency with an increase in temperature. There are no uncontinuous changes of mode frequency in the temperature range studied. It indicates the stable character of static distortions of crystal structure relying on changes of octahedra tilt angle.     

Dielectric and piezoelectric properties of non-stoichiometric (K0.5Na0.5)(Nb0.9+xTa0.1)O3 ceramics

In the study, in order to develop the lead-free piezoelectric ceramics for actuator, transformer and other electronic-devices application, (K_0.5Na_0.5)(Nb_0.9+xTa_0.1)O₃ + 0.5 mol% CuO + 0.2 mol% MnO₂ ceramics were prepared by conventional mixed oxide method. The effects of B-site non-stoichiometry in [(K_0.5Na_0.5)] [(Nb_0.9+xTa_0.1)O₃] ceramics on microstructure and piezoelectric properties were investigated. The density, electromechanical coupling factor (k_p), mechanical quality factor (Q_m), piezoelectric constant (d₃₃), T_C and T_O-T of NKNT ceramics with x = 0.0065 showed the optimum values of 4.58 g/cm³, 0.427, 1554, 109 pC/N, 373 °C and 226 °C, respectively, suitable for piezoelectric motor, and transformer applications.     

Ferroelectric-relaxor behavior of (Na0.5K0.5)NbO3-based ceramics

We report that ferroelectric-relaxor behavior is induced by doping of SrO and TiO₂, or BaO and TiO₂ into classic ferroelectric (Na_0.5K_0.5)NbO₃. It is found that [(Na_0.5K_0.5)_0.9Sr_0.1](Nb_0.9Ti_0.1)O₃ ceramics exhibit a pronounced ferroelectric-relaxor behavior, comparable to that of [(Na_0.5K_0.5)_0.9Ba_0.1](Nb_0.9Ti_0.1)O₃ ceramics. Our results indicate that the relaxor behavior is closely related to the appearance of micropolar regions in these systems. The relaxor behavior should arise from the dynamic response of micropolar clusters. Raman spectra of [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics measured in the wavenumber range from 100 to 1200 cm⁻¹ confirm that the first order scattering is dominant in phonon bands should result from both short-range ordered region (micropolar regions) and disordered matrix. The frequency dependence of dielectric permittivity measurements show that the relaxor behavior of SrO and TiO₂, or BaO and TiO₂ doped (Na_0.5K_0.5)NbO₃ ceramics is not a Debye type in the radio frequency range.     

Dielectric and piezoelectric properties of barium-modified Aurivillius-type Na0.5Bi4.5Ti4O15

In this study, monophasic Ba_x(Na_0.5Bi_0.5)_1−xBi₄Ti₄O₁₅ (x=0.03, 0.06, 0.09 and 0.12) ceramics fabricated from the powders synthesized via the solid-state reaction route exhibited relaxor behavior. X-ray diffraction analysis revealed that the barium-modified Na_0.5Bi_4.5Ti₄O₁₅ ceramics have a pure four-layer Aurivillius phase structure. Dielectric properties and phase transitions were studied and are explained in terms of lattice response of these ceramics. A shift in ferroelectric–paraelectric phase transition (T_c) to lower temperatures and a corresponding increase in permittivity peak with increasing concentration of Ba²⁺ are also observed. The decrease of orthorhombicity in the lattice structure by the larger Ba²⁺ ion incorporation, indicating an approach of a and b parameters, results in lower Curie temperature. The piezoelectric activity of Na_0.5Bi_4.5Ti₄O₁₅ (NBT) ceramics was significantly improved by the modification of barium. The Curie temperature T_c and piezoelectric coefficient d₃₃ for the composition with x=0.12 were found to be 635 °C and 21 pC/N, respectively. The relationship of polarization with lattice response is discussed.     

Luminescence of Fe3+ in single crystals of LiAl5O8

We have measured the luminescent properties of single crystals of LiAl₅O₈:Fe³⁺. In addition to a zero-phonon line due to Fe³⁺ in A-sites, we have observed another sharp fluorescent line at 699.2 nm which we assign to Fe³⁺ occupying B-sites. The excitation spectrum of the B-site Fe³⁺ shows characteristics similar to those of the A-site Fe³⁺ but are also shifted towards longer wavelengths. The spectra of the single crystals are compared with those of ordered and disordered powder samples.     

Effects of doping site and pre-sintering time on microstructure and magnetic properties of Fe-doped BaTiO3 ceramics

The A-site substituted BaTiO₃ ceramics were prepared by solid-state reaction via partial substitution of Fe for Ba²⁺. By comparison with the B-site substituted sample made under similar conditions, the effect of Fe doping site on microstructure and magnetism was investigated using X-ray diffraction, Mössbauer spectroscopy and vibrating sample magnetometer. It is found that A-site substitution can be realized to a certain extent at 7 at% Fe addition, whereas impurities are observed at higher Fe concentrations. In the nominal (Ba_0.93Fe_0.07)TiO₃ sample, the Fe ions are present as Fe²⁺ and Fe³⁺, respectively, replacing A-site Ba²⁺ and octahedral B-site Ti⁴⁺ in hexagonal perovskite lattice. The double-exchange Fe²⁺-O²⁻-Fe³⁺ interactions produce ferromagnetism well above room temperature, but the saturation magnetization and the Curie temperature are both obviously lower than those for B-site substitution due to different magnetic exchange mechanisms. In the B-site substituted sample Ba(Ti_0.93Fe_0.07)O₃, the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti⁴⁺ sites are responsible for ferromagnetism. These results mean that B-site substitution is a better way for Fe-doped BaTiO₃ system to obtain high-Curie-temperature ferromagnetism. Moreover, increasing pre-sintering time can further improve the magnetism of B-site substituted samples, through which the saturation magnetization for Ba(Ti_0.93Fe_0.07)O₃ is enhanced ∼6 times.     

Thermal, electrical, and electrochemical properties of Lanthanum-doped Ba0.5Sr0.5 Co0.8Fe0.2O3-δ

Crystal structure, thermogravimetry (TG), thermal expansion coefficient (TEC), electrical conductivity and AC impedance of (Ba_0.5Sr_0.5)_1-xLa_xCo_0.8Fe_0.2O_3-δ (BSLCF; 0.05?x?0.20) were studied in relation to their potential use as intermediate temperature solid oxide fuel cell (IT-SOFC) cathode. A single cubic pervoskite was observed by X-ray diffraction (XRD). The TEC of BSLCF was increasing slightly with the increasing content of La, and all the compounds showed abnormal expansion at high temperature. Proved by the TG result, it was associated with the loss of lattice oxygen. The electrical conductivity, which is the main defect of Ba_0.5Sr_0.5 Co_0.8Fe_0.2O_3-δ (BSCF), was improved by La doping, e.g., the compound of x=0.20 demonstrated a conductivity of σ=376 S cm⁻¹ at 392 °C. The increase of electrical conductivity resulted from the increased concentration of charge carrier induced by La doping. In addition, the AC impedance revealed the better electrochemical performance of BSLCF. For example, at 500 °C, the sample with composition x=0.15 yielded the resistance values of 2.12 Ω cm², which was only 46% of BSCF.     

Microstructure and piezoelectric properties of Bi0.5(Na0.82K0.18)0.5TiO3−NaSbO3 ceramics

Lead-free piezoelectric ceramics (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ have been prepared by a conventional ceramics technique, and their microstructure and electrical properties have been investigated. The addition of NaSbO₃ has no remarkable effect on the crystal structure within the studied doping content; however, an obvious change in microstructure took place. With increase in NaSbO₃ content, the temperature from a ferroelectric to antiferroelectric phase transition increases, and the temperature for a transition from antiferroelectric phases to paraelectric phases changes insignificantly. Simultaneously, the temperature range between the rhombohedral phase transition point and the Curie temperature point becomes smaller. The piezoelectric properties significantly increase with increase in NaSbO₃ content and the piezoelectric constant and electromechanical coupling factor attain maximum values of d₃₃=160 pC/N and k_p=0.333 at x=0.01. The results indicate that (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ ceramic is a promising lead-free piezoelectric candidate material.     

Na0.5K0.5NbO3-BiFeO3 lead-free piezoelectric ceramics

Lead-free (Na_0.5K_0.5)NbO₃-based piezoelectric ceramics were successfully fabricated by substituting with a small amount of BiFeO₃ (BF). Difficulty in sintering of pure NKN ceramics can be eased by adding a few molar percent of BF, and the crystalline structure is also changed, leading to a morphotropic phase boundary (MPB) between ferroelectric orthorhombic and rhombohedral phases. The MPB exists near the 1-2 mol% BF-substituted NKN compositions, exhibiting enhanced ferroelectric, piezoelectric, and electromechanical properties of P_r=23.3 μC/cm², d₃₃=185 pC/N, and k_p=46%, compared to an ordinarily sintered pure NKN ceramics. The MPB composition has a Curie temperature of ∼370 °C, comparable to that of some commercial PZT materials.     

Evolution of structural and electrical properties of (K,Na,Li)(Nb,Ta,Sb)O3 lead-free piezoceramics through CoO doping

Doping with transition metals is widely used for piezoceramic improvement. In this work, we study the effects of cobalt doping on the properties of the well known (K,Na,Li)(Nb,Ta,Sb)O₃ piezoelectric ceramics. Two different situations were observed: for low concentrations, Co²⁺ cations occupy the A-site of the perovskite structure, whereas for high concentrations they occupy the B-site. The piezoelectric properties of the material are slightly affected with the cobalt concentration, whereas the mechanical quality factor increases by a factor of nearly three.     

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K0.5Na0.5NbO3- 0.04LiSbO3 lead-free piezoelectric ceramics

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K0.5+xNa0.5+xNbO3- 0.04LiSbO3 lead-free piezoelectric ceramics were examined for 0 ≤ x ≤ 0.02. The piezoelectric coefficients exhibited a maximum, d33 = 187 pC/N at x = 0.0075, coinciding with the maximum of the grain size and the apparent density at x = 0.0075. The apparent density and the piezoelectric coefficients decreased with increasing x at higher x which was likely due to the crystal geometrical distortion of 0.96K0.5+xNa0.5+xNbO3-0.04LiSbO3. In addition, super-large grains were found and this may be due to liquid phase sintering. Excess (K++Na+) attracted a sum of space charges to keep the charge neutral, resulting in charge leakage during the course of ceramic polarization, influencing the piezoelectric and ferroelectric properties. These findings are of importance for guiding the design of K0.5Na0.5NbO3-based lead-free ceramics with enhanced electrical properties.     

Ferroelectric properties of Pr6O11-doped Bi4Ti3O12

Praseodymium doped Bi₄Ti₃O₁₂ (BIT) ceramics with composition Bi_2.9Pr_0.9Ti₃O₁₂ (BPT) were prepared by solid state reaction. These samples have polycrystalline Bi-layered perovskite structure without preferred orientation, and consist of well-developed plate-like grains with random orientation. Pr doping into BIT causes a large shift of the Curie temperature (T_C) of the BIT from 675 to 398 °C. At an electric field of 87 kV/cm, the remanent polarization and the coercive field of the BPT ceramics are 30 μC/cm² and 52 kV/cm, respectively. Furthermore, the dielectric permittivity and the dissipation factor of the BPT ceramics are 300 and 0.003 at 1 MHz, 1 V, and room temperature. Ferroelectric properties of the BPT ceramics are superior to V-doped Bi₄Ti₃O₁₂ (∼20 μC/cm² and 80 kV/cm) and (Sr, Ta)-doped Bi₄Ti₃O₁₂ (∼12 μC/cm² and 71 kV/cm) ceramics. In addition, the dense ceramics of praseodymium-doped B₄Ti₃O₁₂ were obtained by sintering at 1100 °C, about 100-200 °C lower than those of the SrBi₂Ta₂O₉ system.     

Study on dielectric and magnetic properties of Ho3Fe5O12 ceramics

Ho₃Fe₅O₁₂ ceramics with garnet structure were prepared by the solid-state reaction method. The results revealed the existence of Fe²⁺ ions have intensive influence on dielectric and magnetic properties of Ho₃Fe₅O₁₂ ceramics, which could be further confirmed by oxygen treatment. With a magnetic field lower than 10 kOe, the ME coefficient reaches 33 ps m⁻¹ at room temperature. And the ME coupling was further verified by dielectric anomaly near Néel temperature.     

Optical properties of (ZnO)0.5(P2O5)0.5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Binary (ZnO)_0.5(P₂O₅)_0.5 glasses doped with Eu₂O₃ and nanoparticles of Gd₂O₃:Eu were prepared by conventional melt-quench method and their luminescence properties were compared. Undoped (ZnO)_0.5(P₂O₅)_0.5 glass is characterized by a luminescent defect centre (similar to L-centre present in Na₂O-SiO₂ glasses) with emission around 324 nm and having an excited state lifetime of 18 ns. Such defect centres can transfer the energy to Eu³⁺ ions leading to improved Eu³⁺ luminescence from such glasses. Based on the decay curves corresponding to the ⁵D₀ level of Eu³⁺ ions in both Gd₂O₃:Eu nanoparticles incorporated as well as Eu₂O₃ incorporated glasses, a significant clustering of Eu³⁺ ions taking place with the latter sample is confirmed. From the lifetime studies of the excited state of L-centre emission from (ZnO)_0.5(P₂O₅)_0.5 glass doped with Gd₂O₃:Eu nanoparticles, it is established that there exists weak energy transfer from L-centres to Eu³⁺ ions. Poor energy transfer from the defect centres to Eu³⁺ ions in Gd₂O₃:Eu nanoparticles doped (ZnO)_0.5(P₂O₅)_0.5 glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between luminescent centre and Eu³⁺ ions.     

Co57 and Fe57 mössbauer studies of the spinels FeCo2O4 and Fe0.5Co2.5O4

Mössbauer source and absorber spectra of FeCo₂O₄ and Fe_0.5Co_2.5O₄ have been obtained between 82 and 523 K. Interpretation of the spectra allow the cation distributions of the compounds to be determined. FeCo₂O₄ is Co²⁺_0.55Fe³⁺_0.45[Co²⁺_0.45Fe³⁺_0.55Co³⁺_1.0]O₄ and Fe_0.5Co_2.5O₄ is Co₁²⁺[Fe³⁺_0.5Co³⁺_1.5]O₄. Spinel tetrahedral site quadruple splitting is observed in both compounds.     

Microwave dielectric properties of high quality factor La(Mg0.5−xCaxSn0.5)O3 ceramics

The microwave dielectric properties of La(Mg_0.5−xCa_xSn_0.5)O₃ ceramics were examined with a view to their exploitation for wireless communications. The La(Mg_0.5−xCa_xSn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The La(Mg_0.5−xCa_xSn_0.5)O₃ ceramics contained Ca₂SnO_4, CaSnO₃, and La₂O₃. The amount of Ca₂SnO₄ increased with increasing sintering temperature. However, the relative amount of CaSnO₃ decreased with increasing sintering temperature. An apparent density of 6.52 g/cm³, a dielectric constant (ε_r) of 20.2, a quality factor (Q×f) of 80,500 GHz, and a temperature coefficient of resonant frequency (τ_f) of −79 ppm/°C were obtained for La(Mg_0.4Ca_0.1Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h.     

K0.5Na0.5NbO3-LiSbO3-BiFeO3/CuFe2O4复合陶瓷的制备与磁电性能研究

采用传统的固相法制备了(1-x)(K_0.5Na_0.5NbO₃-LiSbO₃-BiFeO₃)-xCuFe₂O₄ (x=0.1, 0.2, 0.3, 0.4) 磁电复合陶瓷, 并借助X射线衍射仪、扫描电镜和磁电耦合系数测试仪等对复合陶瓷的微结构和性能进行了分析. 结果表明, 复合陶瓷的K_0.5Na_0.5NbO₃-LiSbO₃-BiFeO₃和CuFe₂O₄物相之间发生了一定的离子相互扩散作用, 且两相的颗粒大小匹配性较好. 随着CuFe₂O₄含量增加, 复合陶瓷的压电系数从130 pC/N减小到30 pC/N, 饱和磁致伸缩系数从4.5×10^-6增加到12.4×10^-6左右, 磁电耦合系数表现出先增加后减小, 在x=0.3时获得最大的磁电耦合系数9.4 mV·cm^-1·Oe^-1. 关键词： 0.5Na_0.5NbO₃-LiSbO₃-BiFeO₃')" href="#">K_0.5Na_0.5NbO₃-LiSbO₃-BiFeO₃ 2O₄')" href="#">CuFe₂O₄ 磁电耦合     

Ferroelectric properties of Pr and Nb co-substituted Sr0.8Bi2.2Ta2O9 thin films

Thin film of both A- and B-site co-substituted Sr_0.8Bi_2.2Ta₂O₉ (SBT) by Pr³⁺ and Nb⁵⁺, i.e. Sr_0.8Pr_0.1Bi_2.1Ta_1.5Nb_0.5O₉ (SPBTN) was fabricated on Pt/Ti/SiO₂/Si substrates by metalorganic decomposition method. The Nb⁵⁺ substitution at B-site and Pr³⁺ substitution at A-site enhanced the remanent polarization and reduced the coercive field of the films, respectively. The remanent polarization (2P_r) value of the SPBTN film was 22 μC/cm². The coercive field (2E_c) value of the SPBTN film was 102 kV/cm, which was much lower than that of SBTN (165 kV/cm). The effects of substitution on structural and ferroelectric properties of SBT were discussed in detail. As a result, the A- and B-sites co-substitution may be one of the promising ways to improve ferroelectric properties of SBT.     

Prediction of defect structure in lithiated tin- and titanium-doped α-Fe2O3 using atomistic simulation

The defect structure of lithiated tin- and titanium-doped α-Fe₂O₃ has been assessed using interatomic potential calculations. Of the models considered for lithiation, a model in which Li⁺ occupies an interstitial site balanced by the reduction of Fe³⁺ to Fe²⁺ on an Fe³⁺ site was found to be more favourable than the substitution of Li⁺ on an Fe³⁺ octahedral site balanced by an O²⁻ vacancy. Insertion of lithium into the interstitial site between two adjacent M⁴⁺ ions was particularly favourable. The calculated lattice parameters decrease on lithiation as has been observed experimentally.