Synthesis and characterizations of BNT–BT–KNN ceramics for energy storage applications

Dielectric, ferroelectric and piezoelectric properties of the (0.94–x) Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–xK_0.5Na_0.5NbO₃/BNT–BT–KNN ceramics with x = 0.02 and 0.05 (2KNN and 5KNN) were studied in detail. Dielectric study and temperature-dependent polarization hysteresis loops indicated a ferroelectric-to-antiferroelectric transition at depolarization temperature (T_d). The low T_d in both the ceramic samples suggested the dominant antiferroelectric ordering at room temperature (RT), which was also confirmed by RT polarization and strain hysteresis loops studies. Antiferroelectric-to-paraelectric phase transition temperature (T_m) was nearly same for both systems. The 5KNN ceramic samples showed the relaxor behaviour. The values of the dielectric constant, T_d, and maximum strain percentage increased, whereas the coercive field and remnant polarization decreased with the increase of the KNN percentage in the BNT–BT–KNN system. High-energy storage density ～0.5 J/cm³ at RT hinted about the suitability of the 5KNN system for energy storage applications.     

Uniaxial stress dependence of ferroelectric properties of xPMN-(1–x)PZT ceramic systems

Effects of uniaxial compressive pre-stress on the ferroelectric properties of ceramics in the PMN-PZT system are investigated. The ceramics with a formula xPb(Mg_1/3Nb_2/3)O₃-(1-x)Pb(Zr_0.52Ti_0.48)O₃ or xPMN-(1-x)PZT when x=0.0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0 are prepared by a conventional mixed-oxide method. The ferroelectric properties under the uniaxial compressive pre-stress of the PMN-PZT ceramics are observed at the stress levels up to 13 MPa using a compressometer in conjunction with a modified Sawyer–Tower circuit. It is found that with increasing compressive pre-stress levels the area of the ferroelectric hysteresis (P–E) loops, the saturation polarization (P_sat), the remanent polarization (P_r), and the coercive field (E_c) decrease. These results are interpreted through the non-180° ferroelastic domain-switching processes. Finally, the calculated differential permittivity for all the xPMN-(1-x)PZT ceramics, except for 0.5 PMN-0.5 PZT, decreases with increasing applied stress. PACS 77.22.Ch; 77.84.Dy     

Dielectric,structural and specific heat properties of lead-free [(1−x)(Na0.5Bi0.5)−xBa]Zr1−yTiyO3 ceramics (x = 0.06, 0.085, 0.09, 0.1 and y = 0.97)

Lead-free [(1?x)(Na_0.5Bi_0.5)?xBa]Zr_1?yTi_yO₃ ceramics (x = 0.06, 0.085, 0.09, 0.1 and y = 0.97) have been prepared by solid-state hot-pressing sintering process. The obtained samples reveal perovskite structure. Structural, thermal expansion, heat capacity, ferroelectric and dielectric measurements have been carried out on these samples in a wide temperature range. The broad anomalies were observed in thermal expansion and heat capacity, which approximately correspond to a structural, ferroelectric and dielectric properties anomaly. These anomalies can be related to temperature features of polar regions and a formation of long-range-order ferroelectric phase. The determined Burns temperature was found to increase with increasing Ba content. The obtained results are discussed in terms of local electric and strain fields caused by a difference in the ionic radii of (Na,Bi) and Ba, and Ti and Zr ions. The NBT–BTZ system is expected to be a new promising candidate for lead-free electronic ceramics.     

Preparation and ferroelectric properties of pyrochlore-free Pb(Ni1/3Nb2/3)O3-based solid solutions

Polycrystalline ceramics of the perovskite solid solution 0.5Pb(Ni_1/3Nb_2/3)O₃-(0.5-x)-Pb(Zn_1/3Nb_2/3)O₃–xPb(Zr_1/2Ti_1/2)O₃; x=0.0–0.5 (PNN–PZN–PZT) were synthesized by a modified columbite method. Highly dense ceramics lacking parasitic pyrochlore phases were prepared at a calcination temperature of 950 °C by using a double-crucible configuration, excess PbO (2 mol %), and a fast heating/cooling rate (20 °C/min). The ceramics were characterized by a variety of techniques including X-ray diffraction, ferroelectric hysteresis loop measurements, field-induced longitudinal strain measurements, and electron microscopy. It was observed that the remanent polarization exhibited a significant increase with increasing x. In addition, the squareness of the hysteresis loop increased quasi-linearly as the molar fraction of PZT increased. The maximum spontaneous polarization and remanent polarization for the x=0.5 composition were 31.9 μC/cm² and 25.2 μC/cm², respectively. Moreover, the data were analyzed to show the evolution of the micro-domain state as a function of the molar fraction of PZT. PACS 77.22.-d; 77.80.Bh; 77.84.Dy; 61.10.Nz; 77.80.Dj     

Ferroelectric properties of Pb(Zr1/2Ti1/2)O3–Pb(Zn1/3Nb2/3)O3 ceramics under compressive stress

Effects of compressive stress on the ferroelectric properties of ceramics in PZT–PZN system were investigated. The ceramics with a formula (1−x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Zn_1/3Nb_2/3)O₃ or (1−x)PZT–(x)PZN (x = 0.1–0.5) were prepared by a conventional mixed-oxide method. The ferroelectric properties under the compressive stress of the PZT–PZN ceramics were observed at the stress levels up to 170 MPa using a compressometer in conjunction with a modified Sawyer–Tower circuit. It was found that with increasing compressive stress the area of the ferroelectric hysteresis (P–E) loops, the saturation polarization (P_sat), the remnant polarization (P_r), and the coercive field (E_c) decreased. These results were interpreted through the non-180° ferroelastic domain switching processes.     

Dielectric, ferroelectric, magnetic and magnetoelectric properties of PMN-PT based ME composites

A systematic study of magnetoelectric composite system (x) CoFe₂O₄+(1−x) Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ with x=0, 0.15, 0.30, 0.45 and 1 was carried out. The lattice strain was calculated using Williamson and Hall equation, which depends on the content of constituent phases in composites. The microstructure was studied using scanning electron microscopy. The ferroelectric transition temperature was independent of the content of individual phases, suggesting that the ferroelectric character is maintained in the composite. Observed P–E and M–H loops indicate that the multiferroic nature of magnetoelectric ceramics is dependent on the content of individual phases. The variation of magnetostriction with dc magnetic field was studied. The maximum magnetoelectric voltage coefficient of 7.2 mV/cm Oe is obtained for the synthesized composites. The magnetoelectric measurements are well explained with magnetostrictive behavior of the magnetic phase.     

The effect of CuO and NiO doping on dielectric and ferroelectric properties of Na0.5Bi0.5TiO3 lead-free ceramics

In the present work, lead-free piezoelectric ceramics (Na_0.5Bi_0.5)TiO₃ –xCuO–yNiO (for x = 0.0, 0.02, 0.04 and 0.06) have been prepared by a conventional solid-state reaction method. An investigation of CuO and NiO doping in bismuth sodium titanate (BNT) and a study of the structure, morphology, and dielectric and ferroelectric properties of the NBT–CuNi system have been conducted. Phase and microstructural analysis of the (Na_0.5Bi_0.5)TiO₃ (NBT) based ceramics has been carried out using X-ray diffraction and scanning electron microscopy (SEM) techniques. Field emission scanning electron microscopy (FE-SEM) images showed that inhibition of grain growth takes place with increasing Cu and Ni concentration. The results indicate that the co-doping of NiO and CuO is effective in improving the dielectric and ferroelectric properties of NBT ceramics. Temperature-dependent dielectric studies have also been carried out at room temperature to 400 °C at different frequencies. The NBT ceramics co-doped with x = 0.06 and y = 0.06 exhibited an excellent dielectric constant ?_r = 1514. The study suggests that there is enormous scope of application of such materials in the future for actuators, ultrasonic transducers and high-frequency piezoelectric devices.     

Phase transition and linear thermal expansion of (Pb1− x Ba x )ZrO3 ceramics

(Pb_{1? x} Ba _x )ZrO₃ ceramics for the composition range 0?≤?x?≤?0.30 were prepared by the mixed oxide solid state reaction method. Phase transition was studied by dielectric and dilatometric measurements. The ferroelectric to paraelectric phase transition temperature was progressively shifted to a lower temperature by replacing lead with barium. The x?=?0.20 sample showed the maximum dielectric constant of 16,300 at the transition temperature. For compositions 0?≤?x?≤?0.075, the antiferroelectric to ferroelectric phase transition exhibited a large linear thermal expansion. However, the antiferroelectric to ferroelectric phase transition did not exist for 0.10?≤?x?≤?0.30 samples. A phase diagram for PBZ ceramics prepared by the conventional mixed oxide method was also present.     

The effect of some transition metal oxides on the physical properties of K0.5Na0.5Nb0.95Ta0.05O3 ceramics

Abstract

Both K_0.5Na_0.5Nb_0.95Ta_0.05O₃ (KNNTO) and (K_0.5Na_0.5Nb_0.95Ta_0.05O₃)_0.99-M_0.01, M = Co₃O₄ and Mn₂O₃ (M/KNNTO) Ferromagnetic behaviour was observed for some M/KNNTO compounds. The hardness and compressive strength of all investigated samples are given. Comparisons with similar materials are discussed. Ceramics were synthesised using a solid-state reaction method. X-ray diffraction patterns of all samples revealed that the crystal structure is orthorhombic. Field-emission scanning electron microscopy was performed. Polarisation hysteresis curves indicated a disruption of ferroelectric order with the addition of M into KNNTO ceramics. The dielectric properties of the investigated ceramics have been studied as a function of frequency and temperature.     

Dielectric,thermal and Raman spectroscopy studies of lead-free (Na0.5Bi0.5)1−xSrxTiO3 (x = 0, 0.04 and 0.06) ceramics

ABSTRACT

Lead-free (Na_0.5Bi_0.5)_1?xSr_xTiO₃ (x = 0, 0.04 and 0.06) ceramics with relative densities above 97% were prepared by solid-state synthesis process. Their dielectric, thermal and Raman properties were studied. X-ray diffraction analysis shows perovskite structure with rhombohedral symmetry at room temperature. Sr doping of Na_0.5Bi_0.5TiO₃ (NBT) results in an increase of the dielectric permittivity, diffusing of the permittivity maximum and its shift toward lower temperatures. The temperature of the rhombohedral–tetragonal phase transition indicated by the differential scanning calorimetry (DSC) peak and relaxational dielectric anomaly near the depolarization temperature are also shifted toward lower temperatures. The observed increase and broadening of the permittivity maximum, enhancement of the dielectric relaxation near the depolarization temperature, broadening of the DSC anomaly related to the rhombohedral–tetragonal phase transition and broadening of the Raman bands with increasing Sr content are attributed to the increase of the degree of cationic disorder and evident enhancement of the relaxor-like features in NBT–xST. This enhancement could play a positive role in the improvement of the piezoelectric performance of NBT-based ceramics.     

Double hysteresis loops induced by Mn doping in Pb0.99Nb0.02(Zr0.95Ti0.05)0.98O3 ferroelectric ceramics

Pb_0.99Nb_0.02(Zr_0.95Ti_0.05)_0.98O₃ (PNZT95/5) ceramics with 1 mol% and without Mn doping were prepared via conventional solid state reaction process. X-ray diffraction patterns show that the PNZT95/5 and Mn-doped PNZT95/5 (PNZTM95/5) ceramics, with composition near the boundary of the ferroelectric phase (FE)/antiferroelectric phase (AFE), have a rhombohedral perovskite structure. The ferroelectric behavior of PNZT95/5 ceramics is strongly affected by Mn doping. Without any aging process the PNZTM95/5 ceramics possess double hysteresis loops (P–E loops), whereas the PNZT95/5 ceramics possess normal single hysteresis loops. Due to the defect dipoles formed by effectively negatively charged Mn³⁺ dopants and positively charged O²⁻ vacancies, the PNZTM95/5 ceramics exhibit the double P–E loops. The defect dipole effect has been proved by investigating the P–E loops under different external fields. As a result, the PNZTM95/5 ceramics become “hardened”, exhibiting a high mechanical quality factor (1300).     

Ferroelectricity and ferromagnetism in fine-grained multiferroic BaTiO3/(Ni0.5Zn0.5)Fe2O4 composites prepared by a novel hybrid process

Dense, homogeneous, and fine-grained multiferroic BaTiO₃/(Ni_0.5Zn_0.5)Fe₂O₄ composite ceramics are synthesized by a novel powder-in-sol precursor hybrid processing route. This route includes the dispersion of nanosized BaTiO₃ ferroelectric powders prepared via conventional sold-state ceramic process into (Ni_0.5Zn_0.5)Fe₂O₄ ferromagnetic sol-gel precursor prepared via a sol-gel wet chemistry process. The composite ceramics show coexistence of obvious ferroelectric and ferromagnetic hysteresis loops at room temperature. Very low dielectric loss of about 0.02–0.0067 in the range of 10 kHz–10 MHz can be achieved, which is about an order of magnitude lower than the results of many reports using conventional processes at room temperature. The combination of high permeability and permittivity with low losses in the ceramics enables significant miniaturization of electronic devices based on the ceramics.     

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.     

Dielectric properties of potassium–sodium niobate ceramics at low frequencies

ABSTRACT

A study of the effects of ageing history on the electrical properties of lead-free ferroelectric ceramics of (K_0.5Na_0.5)(Nb_1?xSb_x)O₃ + 0.5 mol% MnO₂ and (K_0.5Na_0.5)(Nb_1?xTa_x)O₃ + 0.5 mol%MnO₂ for x = 0.05 is reported. The samples after storage at a constant temperature have been subject to infra-low-frequency electric field and radiation. Differences of the photoelectric response between the two examined compounds were found and the restoration of polarisation in the aged ceramic materials by cycles of applied field is discussed.     

锰掺杂对Ba(Zr,Ti)O3陶瓷压电与介电性能的影响

采用氧化物固相反应法制备了锰掺杂改性的Ba(Zr_0.06Ti_0.94)O₃陶瓷.研究了锰的掺杂量对Ba(Zr_0.06Ti_0.94)Mn_xO₃ (BZTM)陶瓷的结构、介电和压电性能的影响.实验发现,当锰含量x<0.5 mol%时进入晶格,使材料压电性能提高,损耗减小,表现出受主掺杂的特性;当锰含量x>0.5 mo 关键词： Ba(Zr 3 陶瓷')" href="#">Ti)O₃ 陶瓷 锰掺杂 介电性能 压电性能     

Effect of bismuth deficiency on structure and electrical properties of (Na0.5Bi0.5)0.93Ba0.07TiO3 ceramics

(Na_0.5Bi_x)_0.93Ba_0.07TiO₃ (x=0.500-0.492) ceramics were prepared by a citrate method, and the structure and electrical properties of the ceramics were investigated with respect to the amount of Bi deficiency. It was detected that the Bi deficiency had a considerable impact on the crystal structure and microstructure. The inspection of both the temperature dependence of the dielectric properties (free permittivity ε₃₃^T/ε₀ and dielectric loss tan δ) and the evolution of the polarization-electrical field (P-E) hysteresis loops with measuring temperature suggests that the Bi deficiency served to increase the depolarization temperature (T_d). The Bi deficiency led to an increase in the coercive field (E_c) and mechanical quality factor (Q_m) together with a decrease in the remanent polarization (P_r) and piezoelectric constants (d₃₃). The variation of the structure and electrical properties with Bi deficiency amount was qualitatively interpreted in terms of the formation of Bi and oxygen vacancies in the Bi-deficient specimens. This research indicates the importance of adequately controlling Bi stoichiometry of (Na_0.5Bi_0.5)_0.93Ba_0.07TiO₃ ceramics in obtaining the desired ferroelectric and piezoelectric properties.     

Influence of sintering conditions on structural,thermal, electric and ferroelectric properties of Na0.5Bi0.5TiO3 ceramics

Na_0.5Bi_0.5TiO₃ ceramics were prepared by a conventional solid-state reaction method and by a hot-pressing route. The influence of sintering conditions on structural, thermal, dielectric and ferroelectric properties of these ceramics was investigated. All obtained samples exhibited a single perovskite phase. It was shown that the sintering conditions significantly influence the properties under investigation. This includes changes in the value of the electric permittivity ? and dielectric loss tanδ, a shift of T_m and T_d and change of the ferroelectric properties. These effects are mainly related to volatility of the Na and Bi components during the sintering process along with formation of their compensating charge defects, which leads to local structure change.     

Phase diagram of (1−x%)(0.89Bi0.5Na0.5TiO3–0.06BaTiO3–0.05K0.5Na0.5NbO3)–x%MnO2 lead-free anti-ferroelectric ceramics

A phase diagram for the lead-free ceramics in the (1?x%)(0.89Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–0.05K_0.5Na_0.5NbO₃)–x%MnO₂ (BNBKN-x%Mn) binary system is constructed for the first time based on the ferroelectric and dielectric measurements. The ferroelectric behaviors under different temperatures suggest that the ceramics are basically of relaxor anti-ferroelectric nature near room temperature. The temperature dependent dielectric properties show that when the addition of MnO₂ increases, the relaxor anti-ferroelectric phase can be stabilized to be close to the Curie point, which corresponds to a relaxor anti-ferroelectric to paraelectric phase transition.     

La诱导(Pb(1-3x/2)Lax)(Zr0.5Sn0.3Ti0.2)O3反铁电介电弛豫研究

采用标准电子陶瓷工艺制备了(Pb_(1-3x/2)La_x)(Zr_0.5Sn_0.3Ti_0.2)O₃(PLZST,0.00≤x≤0.18)反铁电陶瓷,利用X射线衍射、不同频率下弱场介电温谱、强场下的极化强度-电场(P-E)测试研究了材料相结构和电学性能.实验结果发现,随La含量x增大,室温下材料由铁电三方相(关键词： 反铁电陶瓷 介电频率色散 相变弥散 介电弛豫     

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.