Lead-free ceramics based on alkaline niobate tantalate antimonate with excellent dielectric and piezoelectric properties

This paper reports lead-free (Na_0.52K_0.48−x)(Nb_0.94−xSb_0.06)O₃-xLiTaO₃ compositions with significantly enhanced piezoelectric properties. The 6% Sb substituted Na_0.52K_0.48NbO₃ was modified by a small amount of LiTaO₃, leading to the formation of a morphotropic phase boundary between orthorhombic and tetragonal phases in the range of x = 0.035-0.04 where the materials show a strong compositional dependence of various electrical properties. Excellent properties of d₃₃ = 335 pC/N, k_p = 53%, , Q_m = 41 and T_c = 291 °C were obtained in the composition with x = 0.04, indicating that the ceramics studied are promising as a lead-free piezoelectric candidate.     

Sintering, microstructure and piezoelectric properties of CuO and SnO2 co-modified sodium potassium niobate ceramics

The CuO and SnO₂ co-modified Na_0.52K_0.48NbO₃ ceramics were prepared by a conventional mixed oxide method. Densification can be further improved but the grain growth is inhibited as a small amount of SnO₂ is added into 1% CuO doped Na_0.52K_0.48NbO₃. The results indicate that the physical and various electrical properties of CuO and SnO₂ doped Na_0.52K_0.48NbO₃ ceramics significantly depend on sintering conditions and the content of dopants. The ceramics doped with 1 mol% CuO and 1 mol% SnO₂ sintered at 1070 °C for 3 h show improved dielectric and piezoelectric properties: d₃₃ = 120 pC/N, k_p = 0.38, Q_m = 1040, ?_r = 710 and tanδ = 0.013 (1 kHz), in comparison with un-doped or CuO doped compositions.     

Dielectric properties of lead indium niobate ceramics synthesized by conventional solid state reaction method

Pyrochlore free lead indium niobate ceramics are successfully prepared using wolframite precursor by conventional solid state reaction method in air atmosphere, by adding an excess amount of MgO in PbO-InNbO₄ mixture. The dielectric properties of lead indium niobate ceramic studied as a function of both temperature and frequency indicate relaxor ferroelectric behavior with maximum dielectric constant of 4310 at 40 ^οC for 1 kHz. Lowering of transition temperature and enhancement of dielectric constant at room temperature, compared to earlier reports, may be due to the diffusion of magnesium ion into the lead indium niobate. The saturation polarization P_s, measured at room temperature, is found to be 22.5 μC/cm² for 40 kV/cm.     

Piezoelectric and ferroelectric properties of K0.5Na0.5NbO3 ceramics synthesized by spray drying method

Potassium-sodium niobate was synthesized at 800 °C for 1 h using dried precursors in a powder form obtained by the spray drying method. Different samples were sintered from 1060 to 1120 °C for 2 h reaching a relative density as high as 96% of the theoretical value. Piezoelectric and ferroelectric properties were studied for these samples and some of the most prominent results are: k_p, d₃₁, 2P_r, and 2E_C of 0.36, 39 pC/N, 29 μC/cm² and 16.5 kV/cm, respectively, for the sample sintered at 1080 °C. The methodology presented in this study can be used to synthesize submicrometer powders.     

Dielectric characteristics of bismuth-modified lead magnesium niobate ceramics

Aliovalent Bi was substituted for Pb in Pb(Mg_1/3Nb_2/3)O₃ with required alteration in the Mg/Nb ratio. Resultant changes in the perovskite developments, lattice parameters as well as dielectric characteristics were investigated. Powders were prepared via a two-step B-site precursor route to enhance the perovskite formation. The perovskite structure persisted up to the range of 30 mol% Bi(Mg_2/3Nb_1/3)O₃ substitution. Values of the maximum dielectric constant decreased drastically, while the dielectric maximum temperatures changed only moderately. Meanwhile, the diffuseness exponent values decreased continuously with the Bi modification.     

Fabrication of lithium-doped zinc oxide film by anodic oxidation and its ferroelectric behavior

A lithium-doped zinc oxide (ZnO) film was obtained by the anodic oxidation of a zinc sheet in a lithium hydroxide (LiOH) solution under an external DC voltage. The formation of the ZnO film on the surface of the Zn sheet is attributed to two simultaneous processes: the electrochemical oxidation of Zn to ZnO, and the chemical dissolution of ZnO. It was also confirmed that Li element was successfully introduced into the lattice of the ZnO film. The curves of the polarization versus applied field were measured to be hysteresis loops, suggesting ferroelectricity of the Li-doped ZnO film. The remanent polarization and the coercive field of the film were measured to be 4.7 × 10⁻³ C m⁻² and 1.2 × 10⁷ V m⁻¹, respectively. This ferroelectricity is believed to be the result of the occupation of off-centered positions in oxygen tetrahedra by the Li⁺ ions.     

Effect of CeO2 addition on structure and electrical properties of (Na0.5Bi0.5)0.93Ba0.07TiO3 ceramics prepared by citric method

(Na_0.5Bi_0.5)_0.93Ba_0.07TiO₃ ceramics added with 0–0.8 wt.% CeO₂ were prepared by a citrate method, and the influence of the CeO₂ addition on the structure and electrical properties was investigated. The specimens containing various amounts of CeO₂ show the coexistence of rhombohedral and tetragonal phases, with the relative content of the tetragonal phases gradually enhancing with increasing amount of CeO₂. Compared with (Na_0.5Bi_0.5)_0.93Ba_0.07TiO₃, the specimen added with a small amount of CeO₂ (≤0.2 wt.%) display a slightly improved electromechanical coupling factor (k_p) and piezoelectric constant (d₃₃) in conjunction with a reduced dielectric loss (tg δ) and an enhanced mechanical quality factor (Q_m), while higher CeO₂ amounts led to a rapid deterioration of the piezoelectric and ferroelectric properties. The variation of the electrical properties with the CeO₂ addition was tentatively interpreted with respect to doping effect, crystal-structural evolution and stability of ferroelectric domains.     

Influences of poling condition and sintering temperature on piezoelectric properties of (Na0.5Bi0.5)1 − xBaxTiO3 ceramics

The structure, ferroelectric characteristics and piezoelectric properties of (Na_0.5Bi_0.5)_1 − xBa_xTiO₃ (x = 0.04, 0.06, 0.10) ceramics prepared by conventional solid state method were investigated. The influences of poling condition and sintering temperature on the piezoelectric properties of the ceramics were examined. The piezoelectric properties of the ceramics highly depend on poling field and temperature, while no remarkable effect of poling time on the piezoelectric properties was found in the range of 5-25 min. Compared with (Na_0.5Bi_0.5)_0.96Ba_0.04TiO₃ and (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃, the piezoelectric properties of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ are more sensitive to poling temperature due to the relatively low depolarization temperature. Moderate increase of sintering temperature improved the poling process and piezoelectric properties due to the development of microstructural densification and crystal structure. With respect to sintering behavior and piezoelectric properties, a sintering temperature range of 1130-1160 °C was ascertained for (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃.     

Lead zinc niobate (PZN)-barium titanate (BT) ceramics from mechanochemically synthesized powders

Nanosized PZN-BT powders were synthesized directly from their constituent component oxide mixture via a high-energy ball milling process. XRD patterns showed that perovskite phase could be formed after milling for 5 h, while single phase perovskite was achieved when the milling was prolonged for 12 h. Further increase in milling time (20 h) led to the formation of pyrochlore phase. PZN-BT ceramics were obtained by sintering the milled powders at temperatures from 1000 to 1100°C for 1 h. The 1100°C-sintered PZN-BT samples derived from the 12 h milled powders have a density of ∼99% of the theoretical density with an average grain size of about 4 μm, a dielectric constant of 2300 and a dielectric loss of 0.03, being in good agreement with the reported results for PZN-BT prepared by the conventional solid-state reaction process.     

Effect of MnO2 addition on the piezoelectric properties in Pb(Mg1/3Nb2/3)O3 relaxor ferroelectrics

The effects of MnO₂ addition on the piezoelectric properties in Pb(Mg_1/3Nb_2/3)O₃ relaxor ferroelectrics were studied in the ferroelectricity-dominated temperature range from −40 to 30°C. Dielectric, piezoelectric, and electrostrictive properties were examined to clarify the effect of MnO₂ addition. As an added amount of MnO₂ increases, the dielectric constant decreases and the mechanical quality factor increases in Pb(Mg_1/3Nb_2/3)O₃. From the experimental results, it has been found that Mn behaves as a ferroelectric domain pinning element.     

Synthesis and characterization of nanocrystallined zirconia by hydrothermal method

Nano-size zirconia was prepared by hydrothermal method using commercial zirconia powder. XRD study showed that the nano-size zirconia has an appreciable amount of monoclinic phase. The nano-size zirconia obtained has average particle size in the range of 24-36 nm. The SEM of nano-sized zirconia showed diminutively different morphology than the commercial one. TEM micrographs shows well-dispersed monoclinic ZrO₂ nanoparticles. The UV-DRS absorption spectrum of alkali treated zirconia showed an absorption peak at 235 nm (5.3 eV). The FTIR spectrum showed the purity of treated zirconia.     

Rapid formation of lead magnesium niobate-based ferroelectric ceramics via a high-energy ball milling process

Pyrochlore-free nano-sized 0.90Pb(Mg_1/3Nb_2/3)O₃(PMN)-0.10PbTiO₃(PT) and 0.65PMN-0.35PT powders were synthesized from oxides via a high-energy ball milling process. Single perovskite phase PMN-PT were readily formed from the oxide mixture after milling for only 2 h. The grain size calculated from X-ray diffraction (XRD) patterns of all samples is about 20 nm, which is in agreement with the observation from scanning electron microscopy (SEM) (20-50 nm). PMN-PT ceramics were obtained by sintering the milled powders at temperature from 1000 to 1100°C for 2 h. The dielectric, ferroelectric properties of the PMN-PT ceramics derived from the synthesized powders were comparable with the reported results in the literature.     

Ferroelectric and piezoelectric properties of tungsten substituted SrBi2Ta2O9 ferroelectric ceramics

Tungsten substituted samples of compositions SrBi₂(W_xTa_1−x)₂O₉ (x = 0.0, 0.025, 0.050, 0.075, 0.10 and 0.20) were synthesized by solid-state reaction method and studied for their microstructural, electrical conductivity, ferroelectric and piezoelectric properties. The X-ray diffractograms confirm the formation of single phase layered perovskite structure in the samples with x up to 0.05. The temperature dependence of dc conductivity vis-à-vis tungsten content shows a decrease in conductivity, which is attributed to the suppression of oxygen vacancies. The ferroelectric and piezoelectric studies of the W-substituted SBT ceramics show that the remanent polarization and d₃₃ values increases with increasing concentration of tungsten up to x ≤ 0.05. Such compositions with low conductivity and high P_r values should be excellent materials for highly stable ferroelectric memory devices.     

Ferroelectric,dielectric and piezoelectric properties of Sr0.6(BiNa)0.2Bi2Nb2O9 ceramics

Aurivillius-type ceramic, Sr_0.6(BiNa)_0.2Bi₂Nb₂O₉ (SBNBN), was synthesized by using conventional solid-state processing. Phase structure and microstructural morphology were confirmed by X-ray diffraction analyses (XRD) and the scanning electron microscopy (SEM). Dielectric, piezoelectric and electromechanical properties of the SBNBN ceramic were investigated in detail. Curie temperature (T_c), piezoelectric coefficient (d₃₃), electromechanical coupling coefficient k_p, k_t and quality factor Q_m of the SBNBN ceramic were found to be 586.5 °C, 22 pC/N, 5.0%, 8.7% and 651, respectively. In addition, the reasons for varieties of the resistivity and dielectric properties at high temperature were also discussed.     

Role of sintering time,crystalline phases and symmetry in the piezoelectric properties of lead-free KNN-modified ceramics

Lead-free KNN-modified piezoceramics of the system (Li,Na,K)(Nb,Ta,Sb)O₃ were prepared by conventional solid-state sintering. The X-ray diffraction patterns revealed a perovskite phase, together with some minor secondary phase, which was assigned to K₃LiNb₆O₁₇, tetragonal tungsten–bronze (TTB). A structural evolution toward a pure tetragonal structure with the increasing sintering time was observed, associated with the decrease of TTB phase. A correlation between higher tetragonality and higher piezoelectric response was clearly evidenced. Contrary to the case of the LiTaO₃ modified KNN, very large abnormal grains with TTB structure were not detected. As a consequence, the simultaneous modification by tantalum and antimony seems to induce during sintering a different behaviour from the one of LiTaO₃ modified KNN.     

Low temperature sintering and properties of piezoelectric PZT-PFW-PMN ceramics with YMnO3 addition

Low temperature sintering of Pb(Zr,Ti)O₃-Pb(Fe_2/3W_1/3)O₃-Pb(Mn_1/3Nb_2/3)O₃ (PZT-PFW-PMN) quaternary piezoelectric ceramics were studied with the use of YMnO₃ as sintering aid. The sintering aid improved the sinterability of PZT-PFW-PMN ceramics due to the effect of YMnO₃ liquid phase. The effects of YMnO₃ contents and sintering temperature on the phase structure, density, dielectric and piezoelectric properties were investigated. The results show that the sintering temperature can be decreased and the electrical properties can be maintained by the YMnO₃ addition. The optimized properties were obtained by doping 0.30 wt.% YMnO₃ and sintering at 1020 °C, which are listed as follows: d₃₃ = 341 pC/N, K_p = 0.57, Q_m = 1393, tan δ = 0.0053, T_c = 304 °C, P_r = 17.13 μC/cm² and E_c = 11.15 kV/cm, which make this system be a promising material for multilayer piezoelectric actuator and transformer applications.     

Effects of Mn doping on the structure and electrical properties of high-temperature BiScO3-PbTiO3-Pb(Zn1/3Nb2/3)O3 piezoelectric ceramics

The effects of Mn addition on the structure, ferroelectric, and piezoelectric properties of the 0.35BiScO₃-0.60PbTiO₃-0.05Pb(Zn_1/3Nb_2/3)O₃ ceramics were studied. The results demonstrate that the addition of small amounts of Mn did not cause a remarkable change in crystal structure, but resulted in an evident evolution in microstructure and ferro-piezoelctric properties. The addition of Mn can induce combinatory “hard” and “soft” piezoelectric characteristics due to aliovalent substitutions. The optimal electrical properties are obtained in the 0.25 mol% Mn-doped composition with a high Curie temperature, indicating that Mn doping contributes to the electrical properties of the ceramics. It can be expected that the improved piezoelectric material can be a promising candidate for high-temperature piezoelectric applications.     

Dielectric and piezoelectric properties of Y2O3 doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free piezoelectric ceramics

Y₂O₃ doped lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (0-0.7 wt%) were synthesized by the conventional solid state reaction method, and the effect of Y₂O₃ addition on the structure and electrical properties was investigated. X-ray diffraction shows that Y₂O₃ diffuses into the lattice of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ to form a solid solution with a pure perovskite structure. The temperature dependence of dielectric constant of Y₂O₃ doped samples under various frequencies indicates obvious relaxor characteristics different from typical relaxor ferroelectric and the mechanism of the relaxor behavior was discussed. The optimum piezoelectric properties of piezoelectric constant d₃₃ = 137 pC/N and the electromechanical coupling factor k_p = 0.30 are obtained at 0.5% and 0.1% Y₂O₃ addition, respectively.     

Structure, dielectric and ferroelectric anisotropy of Sr2−xCaxBi4Ti5O18 ceramics

Sr_2−xCa_xBi₄Ti₅O₁₈(x = 0, 0.05) powders synthesized by solid state route were uniaxially pressed and sintered at 1225 °C for 2 h. The obtained dense ceramics exhibited crystallographic anisotropy with a dominant c axis parallel to the uniaxial pressing direction which was quantified in terms of the Lotgering factor. Microstructure anisotropy of both compositions (x = 0, 0.05) consisted of plate like grains exhibiting their larger surfaces mostly perpendicular to the uniaxial pressing direction. Dielectric and ferroelectric properties of Sr_2−xCa_xBi₄Ti₅O₁₈ ceramics were measured under an electric field (E) applied parallel and perpendicularly to uniaxial pressing direction. The obtained dielectric ?_R(T) and polarization (P-E) curves depended strongly on E direction thus denoting a significant effect from microstructure and crystallographic texture. Sr_2−xCa_xBi₄Ti₅O₁₈ properties were also significantly affected by Ca content (x): Curie temperature increased from 280 °C (x = 0) to 310 °C (x = 0.05) while ?_R and remnant polarization decreased for x = 0.05. The present results are discussed within the framework of the processing and crystal structure-properties relationships of Aurivillius oxides ceramics.     

一种改性铌酸盐系无铅压电陶瓷的合成与特性研究

K0.5Na0.5NbO3(KNN)系铌酸盐是一类可能替代铅基压电陶瓷的无铅压电陶瓷.利用Ta和Sb掺杂或者取代KNN中的相关离子,在陶瓷的准同型相界(MPB)处显现出高的压电和介电性能.利用传统技术制作出一种新的致密度较高的无铅压电陶瓷(1-x)(K0.5Na0.5)(Nb0.96Sb0.04)O3-xLiTaO3(简记为KNNS-LT).所有的组分在MPB处都存在纯的钙钛矿结构,主要压电性能在MPB处达极大值,其机电耦合系数kp为40%,压电常数d33为225pC/N,居里温度Tc为355℃.