Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3系无铅压电陶瓷的制备工艺研究

利用XRD、SEM等分析技术 ,研究了Na0 .5Bi0 .5TiO3 -K0 .5Bi0 .5TiO3 系无铅压电陶瓷的合成温度 ,烧成工艺条件对陶瓷晶体结构、压电性能的影响。结果表明 ,合成温度提高有利于主晶相的形成 ,适当延长保温时间有利于材料的压电性能。该体系随着KBT含量的增加 ,烧结温度提高 ,烧结温度范围变窄。同时研究了极化工艺条件对材料压电性能的影响表明 ,提高极化电场和适当提高极化温度有利于压电性能的提高 ,但过高的温度由于受到材料高温下退极化的影响而导致材料压电性能变差     

CeO2、Sb2O3掺杂(Na0.88K0.12)0.5Bi0.5TiO3无铅陶瓷的压电性能研究

采用传统陶瓷的制备方法制备了CeO2(0～1.0wt%)和Sb2O3(0～0.6wt%)掺杂的(Na0.88K0.12)0.5Bi0.5TiO3无铅压电陶瓷。运用XRD技术研究了样品的晶体结构,测试并分析了样品的介电、压电性能以及谐振频率温度系数。结果表明:所有组成均呈三方结构的钙钛矿型固溶体特征。在适当掺杂剂用量范围内,压电陶瓷的压电常数、介电常数和介电损耗升高,而平面机电耦合系数降低。CeO2和Sb2O3掺杂均改善了(Na0.88K0.12)0.5Bi0.5TiO3压电陶瓷频率温度稳定性。     

La掺杂(Na0.5Bi0.5)0.82(K0.5Bi0.5)0.18TiO3系统无铅压电陶瓷的制备工艺探讨

采用传统陶瓷工艺，研究了制备[（Na0.5Bi0.5）0.82（K0.5Bi0.5）0.18]1-xLaxTiO3（x=0．00，0．01，0．03，0．05，0．10）无铅压电陶瓷的工艺条件对陶瓷的物相组成、显微结构和压电性能的影响。利用XRD、SEM等技术分析结果表明，合成温度的提高有利于主晶相的形成，且此系统烧成温度范围较窄，故需控制在合适的烧成温度下才能得到高致密度的陶瓷。同时，研究了极化工艺条件对材料压电性能的影响，结果表明，提高极化电场强度、控制适当的极化温度有利于提高材料的压电性能。     

(Na1-xKx)0.5Bi0.5TiO3系的离子挥发性研究

利用固相法制备了(Na1-xKx)0.5Bi0.5TiO3系压电陶瓷,研究其中Bi3 、Na 、K 离子的挥发对其性能的影响。研究结果表明Bi3 的挥发性对样品的性能影响较大,而Na 、K 离子相对较小。     

Bi0.5Na0.5TiO3基无铅压电陶瓷的研究进展

随着经济的发展和人们环保意识的增强,无铅压电陶瓷的研究和开发越来越引起人们的重视.由于钛酸铋钠(Bi0.5Na0.5TiO3,简称为BNT)基无铅压电陶瓷具有良好的铁电性和高的剩余极化引起了广大学者的关注.本文分析了BNT基无铅压电陶瓷的研究进展,其中晶粒取向生长技术是提高其压电性能的一个重要途径.本文还介绍了一种溶剂热法制备织构化BNT基无铅压电陶瓷的方法.     

Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3–SrTiO3陶瓷的准同型相界与电性能

采用固相法制备了 Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3–SrTiO3（NBT–KBT–BT–ST）陶瓷,该体系是按（1–2x）（0.8NBT–0.2KBT）–x（0.94NBT–0.06BT）–x（0.74NBT–0.26ST） （x = 0.10、0.20、0.25、0.30、0.35、0.40、0.45）组合而成的,研究了该系陶瓷的结构与电性能。结果表明：所有样品都处于三方–四方准同型相界区域。该系陶瓷在准同型相界附近表现出了优异的压电性能,压电常数 d33、机电耦合系数 kp和剩余极化强度 Pr随 x 的增加先升高后降低,其中 x=0.35 陶瓷的电性能最佳：d33= 210 pC/N,kp= 0.319,Pr= 39.3 μC/cm2,Ec= 20.2 kV/cm,是一种良好的无铅压电陶瓷候选材料。依据准同型相界组成的线性组合规律来寻找具有优异压电性能的 NBT–KBT–BT–ST 陶瓷准同型相界组成是可行的。     

Na0.5Bi0.5TiO3基无铅压电陶瓷研究与应用的新进展

综述了钙钛矿结构的Na0.5Bi0.5TiO3(简称BNT)基无铅压电陶瓷的研究现状,并与其它无铅基压电陶瓷进行了对比.列举了近年来BNT 基压电陶瓷的新发展和热门体系,结合笔者承担的相关研究工作内容,总结和指出了BNT基无铅压电陶瓷新的研究思路和相关方向.     

Na0.5Bi0.5TiO3基无铅陶瓷的铁电相变和弛豫特性研究进展

综合介绍了Na0.5Bi0.5TiO3（sodium bismuth titanate,NBT）基无铅铁电材料在铁电相变和弛豫特性方面近年来国内外的研究进展。介绍了温度变化对NBT铁电性能的影响以及产生弛豫相变的机理。此外,结合本课题的研究成果,介绍了不同含量BaTiO3和K0.5Bi0.5TiO3及其它化合物取代后对NBT基铁电相变和弛豫特性的影响。指出了在提高压电性能的同时,大幅降低材料铁电一反铁电相变,即材料的退极化温度,可能会影响到压电陶瓷材料的使用温度范围。     

制备工艺对0.95(K_(0.5)Na_(0.5))NbO_3-0.05CaZrO_3基无铅陶瓷压电性能的影响

采用传统陶瓷工艺制备了0.95(K0.5Na0.5)NbO3-0.05CaZrO3无铅压电陶瓷。研究了烧结温度和极化工艺对陶瓷压电性能的影响。结果表明:随着烧结温度的提高,0.95(K0.5Na0.5)NbO3-0.05CaZrO3陶瓷的体积密度增大,在1170℃时达到最大值,同时d33和kp,在此温度也分别达到他们的最大值210pC/N和0.40。极化工艺对0.95(K0.5Na0.5)NbO3-0.05CaZrO3陶瓷的压电性能有明显的影响,0.95(K0.5Na0.5)NbO3-0.05CaZrO3陶瓷的最佳极化温度是70℃,最佳极化电场是4kV/mm。     

Na0.5Bi0.5TiO3-BaTiO3系无铅压电陶瓷的弛豫相变特征和铁电性能

研究了(1-x)Na0.5Bi0.5TiO3-BaTiO3系无铅压电陶瓷的弛豫相变特性和铁电性能。X射线衍射分析表明：当0．06≤x≤0．10时。该体系陶瓷具有三方、四方相共存的晶体结构。通过测试材料的介电温谱分析发现：当x≥0．10时,该体系陶瓷在200℃以上具有弛豫铁电体的特征。通过测试样品在不同温度的电滞回线。认为该体系材料在一定组成范围内随温度的升高存在反铁电中间相。通过研究样品的铁电性能发现：当x=0．10时,材料的矫顽场达到极小值。     

Thermally-stable large strain in Bi(Mn0.5Ti0.5)O3 modified 0.8Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3 ceramics

(1-x)[0.8Bi_0.5Na_0.5TiO₃-0.2Bi_0.5K_0.5TiO₃]-xBi(Mn_0.5Ti_0.5)O₃ (x = 0–0.06, BNKMT100x) lead-free ferroelectric ceramics were prepared via solid state reaction method. Bi(Mn_0.5Ti_0.5)O₃ induces a structure transition from rhombohedral-tetragonal morphotropic phases to pseudo-cubic phase. Moreover, the wide range of compositions within x = 0.03–0.055 exhibit large strain of 0.31%–0.41% and electrostrictive coefficient of 0.027–0.041 m⁴/C². Especially, at x = 0.04, the large strain and electrostrictive coefficient are nearly temperature-independent in the range of 25–100 °C. The impedance analysis shows the large strain and electrostrictive coefficient originate from polar nanoregions response due to the addition of Bi(Mn_0.5Ti_0.5)O₃.     

Raman spectroscopy of Na0.5Bi0.5TiO3

We have measured the Raman spectra of bismuth sodium titanate in its rhombohedral, tetragonal, and cubic phases, with special attention paid to the phase transitions at 584K and 837K (heating). Both transitions appear to be order-disorder and strongly first order, with large thermal hysteresis. The phonon spectra at temperature slightly below the tetragonal phase are remarkably similar to BaTiO₃ with A₁(To) modes at 130, 269, and 541 cm^-1 (compared with 170, 270, 520 cm^-1 in BaTiO₃) and an E(TO) at 52 cm^-1.     

Enhanced pyroelectric response from domain-engineered lead-free (K0.5Bi0.5TiO3-BaTiO3)-Na0.5Bi0.5TiO3 ferroelectric ceramics

Enhanced pyroelectric response is achieved via domain engineering from [001] grain-oriented, tetragonal-phase, lead-free 0.2(2/3K_0.5Bi_0.5TiO₃-1/3BaTiO₃)-0.8Na_0.5Bi_0.5TiO₃ (KBT-BT-NBT) ceramics prepared by a templated grain growth method. The [001] crystallographic orientation leads to large polarization in tetragonal symmetry; therefore, texturing along this direction is employed to enhance the pyroelectricity. X-ray diffraction analysis revealed a Lotgering factor (degree of texturing) of 93 % along the [001] crystallographic direction. The textured KBT-BT-NBT lead-free ceramics showed comparable pyroelectric figures of merit to those of lead-based ferroelectric materials at room temperature (RT). In addition to the enhanced pyroelectric response at RT, an enormous enhancement in the pyroelectric response (from 1750 to 90,900 μC m^?2 K^?1) was achieved at the depolarization temperature because of the sharp ferroelectric to antiferroelectric phase transition owing to coherent 180° domain switching. These results will motivate the development of a wide range of lead-free pyroelectric devices, such as thermal sensors and infra-red detectors.     

Dielectric properties of some low-lead or lead-free perovskite-derived materials: Na0.5Bi0.5TiO3–PbZrO3, Na0.5Bi0.5TiO3–BiScO3 and Na0.5Bi0.5TiO3–BiFeO3 ceramics

Na_0.5Bi_0.5TiO₃ (NBT) and its modifications are known to be new lead-free ferroelectric materials and are promising for environment friendly devices. The systems under investigation were (i) NBT (trigonal/ferroelectric)–PbZrO₃ (orthorhombic/antiferroelectric); (ii) NBT (trigonal/ferroelectric)–BiScO₃ (trigonal/paraelectric); and (iii) NBT (trigonal/ferroelectric)–BiFeO₃ (trigonal/antiferromagnetic).The lattice parameters change as expected from the respective ionic radii values. For NBT–PZ, the dielectric permittivity shows a large frequency and temperature dispersion suggesting a relaxor-like behaviour dependent on the thermal annealing of the samples. For NBT–BS, the Curie temperature increases with BS content as well as the diffuseness of the phase transition, connected with the introduced disorder. For NBT–BF, the overall behaviour of the permittivity of NBT is maintained up to 50% BF but anomalies of the permittivity appeared close to 600 °C, which might be connected with the onset of magnetic influence for high BF content.     

Growth and electrical properties of Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 lead-free single crystals by the TSSG method

A series of NBT-KBT lead-free crystals with dimensions of Φ 35×10 mm were successfully grown by the TSSG method. The as-grown crystals possess rhombohedral perovskite structure at room temperature. The curves ε(T) for all crystals show two abnormal dielectric peaks. The depolarization temperatures T_d derived from the first peak of curves tan δ(T) vary with the KBT content, which are 130, 150, 140, and 115 °C respectively, for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals, being well consistent with the T_d obtained from the temperature dependence of k_t. A notable thermal hysteresis, ΔT≈35 °C, for ferroelectric-antiferroelectric phase transition was also disclosed for 92NBT-8KBT crystal. The investigation of orientation dependence for electrical properties disclosed the dielectric parameters show weak anisotropy. The piezoelectric constants (d₃₃) are 147, 175, 205, 238 pC/N and the values of k_t are 38%, 52%, 52%, 54%, respectively for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals.     

Effect of closed pores on dielectric properties of 0.8Na0.5Bi0.5TiO3-0.2K0.5Bi0.5TiO3 porous ceramics

Porous 0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃ ceramics are fabricated via the pore-forming agent method with polymethyl methacrylate (PMMA) and stearic acid (SA) as pore forming agents, and microstructure observations demonstrate that the porosity, pore shape, and pore sizes can be controlled by the synthesis technology. The dielectric properties of porous ceramics are found not only correlated to the pore-matrix composite model, but also have a significant grain-size effect. Based on the Zener Theory, pining forces exerted by pores on the grain boundary are calculated, to explain the shape effect of pores on grain boundary migration. A phase-field simulation is carried out to investigate pore shape effect on the grain size regulation in porous polycrystalline, and simulation results are in good agreements with experiential results as well as theoretical calculations. Thus, a modified equation is proposed to predict the effective permittivity of the porous piezoelectric ceramics by considering effects of porosity, pore shape and grain size.     

Composition and microstructure of Na0.5Bi0.5TiO3 ceramics with excess Bi

In the present work, Na_0.5Bi_0.5TiO₃ (NBT) ceramics with the addition of excess Bi in two different ways – before calcination and before sintering – are considered, revealing how the excess Bi affects their microstructure and chemical content. Average grain size is seen to decrease, with the grain size distribution becoming less diffused at higher excess Bi concentrations. The reason for such a feature is the shift of the sintering temperature region where the abnormal grain growth starts to contribute towards higher temperatures. The influence of excess Bi is more pronounced in the case if it is added before calcination. It was discovered that a small amount of excess Bi helps to prevent the formation of Bi-deficient inclusions. While, high concentrations of excess Bi induce the formation of Bi-rich inclusions – most probably Na_0.5Bi_4.5Ti₄O₁₅. Possible mechanisms of formation of both types of inclusions are discussed in detail. Instead of Bi over-stoichiometry, elevated Na content and slightly lower O content were detected in the matrix grains of the sintered NBT ceramics prepared with excess Bi. These deviations increase upon increasing the added excess Bi concentration. The presence of another, Na-rich phase, is assumed, which could not be detected by X-ray diffraction or by energy-dispersive X-ray analysis.     

Optical dispersion and bandgap of pure and Mn-doped 0.92Na0.5Bi0.5TiO3-0.08K0.5Bi0.5TiO3 lead-free single crystals

Optical properties of lead-free ferroelectric pure and Mn-doped 0.92Na_0.5Bi_0.5TiO₃-0.08K_0.5Bi_0.5TiO₃ (NBT-8KBT) single crystals have been investigated systematically. Refractive index and extinction coefficient were measured and the critical parameters are obtained by modified Sellmeier dispersion equations and single-oscillator dispersion relation. The decline of refractive index for Mn:NBT-8KBT could be related to the lattice distortion of the Mn ions doping. High transmittance (>70%) over the transparent region (>400 nm) was found in the pure NBT-8KBT, higher than that of Mn:NBT-8KBT, which could be caused by the increase of domain wall density. An about 100 nm red-shift of absorption edge was observed in the Mn:NBT-8KBT single crystal, which is located in the visible region. Optical bandgap energies calculated through Tauc equation and a large bandgap difference of 2.96 and 2.62 eV occurs in the NBT-8KBT and Mn:NBT-8KBT, respectively, which illustrates the modulation of the band structures by Mn doping.     

The influence of Ti-nonstoichiometry in Bi0.5Na0.5TiO3

The influence of Ti-nonstoichiometry in BNT was investigated using XRD, SEM/EDX and electrical measurements. It is shown that nonstoichiometric compositions of BNT derived materials tend to maintain stoichiometry by forming a secondary phase like TiO₂ or by the evaporation of volatile compounds like Bi₂O₃ and Na₂O. Due to this ability, variations of the Ti-content can be used to control the grain size of the material with little impact on electrical properties. The data also implies that the used processing temperatures lead to evaporation approximately 2 mol% of A-site cations during preparation since the sample with 1 mol% Ti-deficiency still shows TiO₂ secondary phase.     

Compositional range and electrical properties of the morphotropic phase boundary in the Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 system

We have investigated the Na_0.5Bi_0.5TiO₃–K_0.5Bi_0.5TiO₃ (NBT–KBT) system, with its complex perovskite structure, as a promising material for piezoelectric applications. The NBT–KBT samples were synthesized using a solid-state reaction method and characterized with XRD and SEM. Room-temperature XRD showed a gradual change in the crystal structure from tetragonal in the KBT to rhombohedral in the NBT, with the presence of an intermediate morphotropic region in the samples with a compositional fraction x between 0.17 and 0.25. The fitted perovskite lattice parameters confirmed an increase in the size of the crystal lattice from NBT towards KBT, which coincides with an increase in the ionic radii. Electrical measurements on the samples showed that the maximum values of the dielectric constant, the remanent polarization and the piezoelectric coefficient are reached at the morphotropic phase boundary (MPB) (? = 1140 at 1 MHz; P_r = 40 μC/cm²; d₃₃ = 134 pC/N).