Effects of pore size and orientation on dielectric and piezoelectric properties of 1-3 type porous PZT ceramics

Porous PZT ceramics have drawn an increasing amount of interest in recent years due to their superior properties compared with the dense material. However, researchers have usually dedicated effort to 0-3 and 3-3 type porous PZT ceramics and little attention has been focused on 1-3 type. The 1-3 type porous PZT ceramics with high porosity were fabricated in this study by freeze-casting process. All samples possessed high piezoelectric coefficient (d₃₃) with high porosity owing to the special one-dimensional ordered porous structure along the poling direction. The d₃₃ values increased by either improving the pore channel orientation level or decreasing pore size. The relative permittivity improved only with the enhancement of pore channel orientation level. The acoustic impedances ranged from 1.45 to 1.35 MRayls which could match well with those of biological tissue or water; therefore, this material would be beneficial in hydrophone applications.     

Piezoelectric and mechanical properties of CaO reinforced porous PZT ceramics with one-dimensional pore channels

The formation of capillaries in sodium alginate gels is a dissipative process driven by unidirectional diffusion of divalent cations into sodium alginate sols. In the present work, we have prepared 3-1 type porous lead zirconate titanate (PZT) ceramics with oxides (CaO) being doped on a molecular level from the dissipative process by incorporating PZT particles into the sodium alginate gel matrix. By varying the concentration of cation solutions (CaCl₂) from 0.5 mol/L to 2.5 mol/L, both the microstructure, doping amount of oxides (CaO) and crystalline phase of the porous PZT ceramics were tailored. Accordingly, increase in the concentration of Ca²⁺ has led to a reduction in the relative permittivity (ε_r) first, and then an increase, while the piezoelectric coefficient (d₃₃ and d₃₁) demonstrated an opposite variation tendency. The prepared samples possessed a maximal HFOM value of 4755×10^–15 Pa⁻¹ when the concentration of Ca²⁺ was 1.0 mol/L. Addition of CaO was found to improve the compressive strength of porous PZT ceramics, which was preferential to promoting the stability and reliability for application.     

Effects of foam composition on the microstructure and piezoelectric properties of macroporous PZT ceramics from ultrastable particle-stabilized foams

Porous lead zirconate titanate (PZT) ceramics could be produced by combining the particle-stabilized foams and the gelcasting technique. In this study, the foaming capacity of particle-stabilized wet foams was tailored by changing the concentration of valeric acid and pH values of suspension. Accordingly, porous PZT ceramics with different porosity, microstructure, dielectric and piezoelectric properties were prepared with the respective wet foam. Increase in the porosity led to a reduction in the relative permittivity (ε_r), a moderate decline in the longitudinal piezoelectric strain coefficient (d₃₃) and a rapid decline in the transverse piezoelectric strain coefficient (d₃₁), which endowed porous PZT ceramics with a high value of hydrostatic strain coefficient (d_h) and hydrostatic figure of merit (HFOM). As a result, the prepared samples possessed a maximal HFOM value of 19,520×10^?15 Pa^?1 with the porosity of 76.3%. The acoustic impedance (Z) of specimens had the lowest value of 1.35 Mrayl, which could match well with those of water or biological tissue; accordingly, the material would be beneficial in underwater sonar detectors or medical ultrasonic imaging.     

Effect of the slurry composition on the piezoelectric properties of PZT ceramics fabricated via materials extrusion 3D printing

Herein, the effect of the binder content in lead zirconate titanate (PZT) slurry has been systematically studied to improve the piezoelectric properties of PZT ceramics prepared via material extrusion 3D printing. For smooth printing, a slurry with a binder concentration ranging from 6 to 12 wt% was proposed. The porosity of the green body first decreased and then increased with an increase in the binder concentration, and the minimum porosity was obtained when the binder concentration reached 10 wt%. Samples with increased density were obtained after debinding and lead-rich atmosphere sintering. PZT piezoceramics fabricated using a binder content of 10 wt% exhibit the maximum relative density (96.9%), largest piezoelectric constant (342.6 pC/N) and dielectric constant (1621). Based on the above process, the wood pile structure and helical twentytetrahedral structural components were successfully fabricated using the material extrusion process. This research lays the foundation for the engineering application of 3D printing to fabricate high-performance piezoceramics with complex shapes.     

Effects of microwave heating on dielectric and piezoelectric properties of PZT ceramic tapes

Commercial lead zirconate titanate (PZT) perovskite powders were used to fabricate ceramic tape and then sintered by microwave and conventional methods. Both dielectric and piezoelectric properties of PZT ceramic tapes were studied in terms of sintering process. X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) show the PZT perovskite phase with smaller grain size and dense microstructure can be obtained at a lower sintering temperature by microwave process. It was also observed that shrinkage ratio and bulk density of the tapes sintered at 800 °C were obtained about 19% and 7.46 g/cm³ by the microwave heating method, respectively, that is corresponding to those values of sintered PZT tapes at 950 °C by conventional process. Moreover, the dielectric constant and maximum permittivity are increased about 30% as compared with conventional processing method. The experimental results demonstrated that the characteristics of the PZT tapes could be significantly improved by microwave heating method. These results demonstrate that such a simple approach can upswing the piezoelectric and dielectric properties of these tapes by using microwave process with a short heating time.     

Impact of ionizing radiation on structural,dielectric, and piezoelectric properties of Sr modified PZT

Ion irradiation effects on piezoceramic (Pb_0.94 Sr_0.04) (Zr_0.52 Ti_0.48)O₃ (PSZT) are investigated by using 4 MeV carbon (C), 9 MeV copper (Cu), and 20 MeV gold (Au) ions. The energies of incident ions are selected in order to target the same range of all incident ions in the material, while producing different amounts of vacancies. The ion irradiation is performed with fluences of 1×10¹³, 1×10¹⁴, and 1×10¹⁵ ions/cm² using Tandem Pelletron accelerator (5UDH-2). Post irradiation changes in PSZT are investigated via various structural, dielectric, and piezoelectric measurement techniques. Results divulge that the irradiation process disturbs the crystallinity along with reduction in X-ray diffraction (XRD) peak intensities owing to strain induced structural defects. A small decrease in dielectric constant is observed due to trapped charges, which screen the depolarization after irradiation. However, a significant decrease is detected in piezoelectric charge coefficients (d₃₃) and piezoelectric voltage coefficients (g₃₃) due to switching of micro domains of PSZT as a result of energy observed during irradiation process. These results indicate that ion irradiation has damaging effects on the properties of PSZT. The discussed information may be utilized to assess performance of PSZT based devices under radiation rich environments such as space.     

Effects of Sm-substitution on dielectric,ferroelectric, and piezoelectric properties of 0.36(Bi1-xSmx)ScO3-0.64PbTiO3 ceramics

Dielectric, ferroelectric, and piezoelectric properties of 0.36(Bi_1-xSm_x)ScO₃-0.64PbTiO₃ (BSPT-xSm) ceramics were investigated to assess effects of Sm-substitution on 0.36BiScO₃-0.64PbTiO₃ for high temperature piezoelectric device application. Optimal sintering was achieved at 1200°C when the BSPT-xSm ceramics were fully densified and crystallized with a perovskite structure without any secondary phase. The substitution of Bi³⁺ with Sm resulted in degradation of rhombohedral side in BSPT-xSm ceramics having morphotropic phase boundary. In addition, variations of grain size and ferroelectric behavior after Sm-substitution were insignificant. However, dielectric constant (ε^T₃₃/ε₀) was significantly enhanced with an increasing of amount of Sm to 5%. Although a slight decrease of relative density in case of x exceeding 3% led to deterioration of piezoelectric values of d₃₃, k_p, and d₃₃*, the BSPT-3%Sm ceramic exhibited excellent values of d₃₃ of 628 pC/N, k_p of 62.4%, and d₃₃* of 718 pm/V at 4.5 kV/mm, along with a high ferroelectric transition temperature of 421°C. The highly increased diffusion coefficient of 1.909 also implies that the Sm-substitution contributed to relaxor-like ferroelectric behavior of BSPT ceramics.     

Effect of sintering aid and repeated sol infiltrations on the dielectric and piezoelectric properties of a PZT composite thick film

Thick PZT films have been produced using a combination of spin coating of a composite slurry and subsequent infiltration of PZT producing sol. The effect of adding a Cu₂O–PbO sintering aid and repeated sol infiltrations have been studied with the aim of producing dense PZT films. Relative permittivity has been shown to increase with the addition of sintering aid and increased levels of sol infiltration. Measurements of piezoelectric properties indicate that sol infiltrations have no effect on d₃₃ once a critical density has been exceeded. A sample with approximately 10% closed porosity was obtained following the incorporation of sintering aid and four infiltration steps per layer. This resulted in a mean relative permittivity of approximately 700 and a d₃₃ of 62 pC/N (poling conditions: 8 V/μm for 5 min at 200 °C).     

Effects of firing temperature on the microstructures and properties of porous mullite ceramics prepared by foam-gelcasting

Porous mullite ceramics were prepared at 1300–1600°C for 2?h via a foam-gelcasting route using industrial-grade mullite powders as the main raw material, Isobam 104 as the dispersing and gelling agent, triethanolamine lauryl sulphate as the foaming agent and sodium carboxymethyl cellulose as the foam stabilising agent. The effects of firing temperature on the sintering behaviour of green samples as well as microstructures and properties of final porous mullite products were investigated. With increasing the temperature from 1300 to 1600°C, linear shrinkage and bulk density values of fired samples increased, whereas their porosity decreased. Mechanical strength and thermal conductivity values of fired samples decreased with increasing their porosities. Even at a porosity level as high as 79.4%, compressive and flexural strengths of fired samples (with average pore size of 314?μm) remained as high as 9.0 and 3.7?MPa, respectively, and their thermal conductivity (at 200°C) remained as low as 0.21?W?(m^?1?K^?1).     

Study of vibratory behavior of interconnected porous PZT by impulse method

Performances in ultrasonic active transducers of interconnected porous lead zirconate titanate (PZT) piezoelectric disks with a porosity ranging from 30 to 70%, and polarized along their axial axis, are investigated. The characterization method used is based on the measurement of the voltage, which appears between the two faces of the piezoelectric element when it is excited by a current impulse. The device used, allows the acquisition of axial and radial vibrations of the transducer, and from these data, electromechanical and acoustic parameters are deduced. One observes that interconnected porosity causes the disappearance of the radial vibrations, and for large porosities the disk vibrates exclusively according to the axial mode. k_t is increased, the acoustic impedance is reduced, and the axial propagation velocity reaches 2500 m s⁻¹ for 30% of porosity. These results show that interconnected porous PZT are suitable for making ultrasonic active transducer, such as biomedical imaging devices.     

A flexible piezoelectric pressure sensor based on PVDF nanocomposite fibers doped with PZT particles for energy harvesting applications

Flexible piezoelectric energy harvesters are a suitable choice for scavenging wasted mechanical energy because of the high demand for sustainable power sources. Flexible pressure sensors based on PVDF-PZT nanocomposite with different PZT volume fractions (0.011, 0.041, 0.096, 0.17, 0.3, and 0.37) were prepared in the form of fibers through an electrospinning method for piezoelectric energy harvesting application. According to the results, dielectric constant and piezoelectric coefficients (e.g. piezoelectric coefficient, and figure of merit) gradually increased with the doping of PZT particles into PVDF fibers. Dielectric constant (ϵ), piezoelectric coefficient (d), and figure of merit (d × g) for PVDF-PZT nanocomposite with 0.011 PZT volume fraction were 37.29, 10.51 pCN⁻¹, and 33.46 × 10⁻¹⁶ m²/N, respectively, and increased to 104.81, 22.93 pCN⁻¹, and 56.68 × 10⁻¹⁶ m²/N for PVDF-PZT nanocomposite fibers with a volume fraction of 0.37. As piezoelectric energy harvesters, piezoelectric sensitivity of PVDF-PZT nanocomposite fibers rose with increasing the PZT volume fraction. The generated output voltage was 184 mV under an applied force of 2.125 N with the piezoelectric sensitivity calculated as 173.507mV/Nμm for PVDF-PZT nanocomposite fibers with 0.37 PZT volume fractions which increased compared to pristine PVDF fibers (generated output voltage = 22 mV under applied force 2.4 N, piezoelectric sensitivity = 29.49 mV/Nμm). The achieved output power density of PVDF-PZT nanocomposite fibers with 0.37 PZT volume fractions was obtained 30.69μW cm⁻² higher than PVDF-PZT nanocomposite fibers with 0.011 PZT volume fractions (18.44μW cm⁻²).     

Hard/soft effects of multivalence co-dopants in correlation with their location in PZT ceramics

Piezoelectric hard/soft effects of multivalence co-dopants (Sb and Mn) in correlation with their location in the lattice, were investigated in PZT ceramics, prepared by conventional ceramic technology, with the following compositions: Pb_0.98Sr_0.02 ((Ti_0.49Zr_0.51)_1-0.015-xMn_0.015Sb_x)O₃ with x = 0, 0.005, 0.01, 0.02, 0.03, where antimony was initially assumed to substitute for Ti/Zr ions. The antimony valence state was found to be +3 in all samples by X-ray Photoelectron Spectroscopy investigations. The Electron Paramagnetic Resonance spectra evidenced a steep enhancement of the Mn²⁺ concentration upon increasing antimony doping level, explained by a charge compensation mechanism, between the Sb³⁺ ions substituting Pb²⁺ at the A-sites and the Mn²⁺ ions, localized at the B-sites. The incorporation of Sb³⁺ at the A-site of the PZT lattice is also supported by the variation of the lattice parameters, determined by X-ray Diffraction, with the increasing Sb concentration. The investigation of the dielectric, electromechanical and ferroelectric properties evidenced a hard piezoelectric behavior, mainly attributed to the presence of large sized Mn²⁺ ions, localized at B-sites. Our results prove that the piezoelectric hard/soft response is decisively influenced by the interplay between multiple valence states and locations of the co-dopants, on one hand, and the charge compensation mechanisms, on the other hand. This provides indirect information about the location of some co-dopants which can substitute for both cationic sites in the PZT based ceramics.     

Enhancement of piezoelectric and ferroelectric properties of BaTiO3 ceramics by aluminum doping

Ferroelectric and piezoelectric properties of BaTiO₃ and Al-doped BaTiO₃ ceramics were investigated. The ferroelectric study demonstrated that, by doping Al³⁺ ions in the A-site of BaTiO₃, the polarization–electric field loop exhibited enhanced remnant polarization (from 12 to 17.5  μC/cm²), saturation and switching. In addition, the piezoelectric constant (d₃₃) increased with Al-doping for both static and dynamic strain values (from 75 to 135 and from 29.2 to 57.9 pC/N, respectively, at a maximum applied electric field of 16 kV/cm). Furthermore, the dielectric constant values increased and both the dielectric loss factor and leakage current decreased, even though the transition temperature shifted to lower temperature (from 121 to 113 °C) for the Al-doped sample. Therefore, the Al-doped BaTiO₃ has adjustable piezoelectric and ferroelectric properties.     

Effects of N2 pressure and Si particle size on mechanical properties of porous Si3N4 ceramics prepared via SHS

Porous silicon nitride ceramics with high flexural strength and high porosity were directly fabricated by self-propagating high temperature synthesis (SHS). The effects of N₂ pressure and Si particle size on the phase composition, microstructure, and mechanical property were investigated. N₂ influences not only the thermodynamics but also the kinetics of the SHS as initial reactant. Flexural strength ranged between 67 MPa and 134 MPa with increasing N₂ pressure. On the other hand, flexural strength ranged from 213 MPa to 102 MPa with different Si particle sizes. This plays an important role on the final diameter and length of β-Si₃N₄ grains and the formation mechanism of porous Si₃N₄ ceramics.     

In-situ reaction synthesis of porous Si2N2O-Si3N4 multiphase ceramics with low dielectric constant via silica poly-hollow microspheres

In the present work, a novel and facile process has been proposed to fabricate porous Si₂N₂O-Si₃N₄ multiphase ceramics with low dielectric constant (ε_r＜4.0). Since silica poly-hollow microspheres could serve as the source of SiO₂ and the pore-forming agent, they have been introduced into Si₃N₄ slurry through the gelcasting technique. This process is benefited from the liquid phase sintering reaction between SiO₂ and Si₃N₄ with the aid of sintering additives, leading to in-situ synthesis of Si₂N₂O phase and porous structure. The content of silica poly-hollow microspheres has great influence on the properties of the final products. It indicates that Si₂N₂O phase would become the major phase when the content of silica poly-hollow microspheres was above 25 wt%. Furthermore, the micromorphology results reveal that the content of pores with many smaller aggregate microspheres increases as microspheres amount rises. As a result, along with the addition of silica poly-hollow microspheres, the bulk density decreases to 1.32±0.01 g/cm³, and open porosity ranges from 28.4±0.4% to 52.0±0.5%. Porous Si₂N₂O-Si₃N₄ multiphase ceramics prepared with 25 wt% silica poly-hollow microspheres addition possess flexural strength of 42.3±3.8 MPa, low dielectric constant of 3.31 and loss tangent of 1.93×10⁻³. It turns out to be an effective method to fabricate porous Si₂N₂O-Si₃N₄ composites with excellent mechanical and dielectric properties, which could be applied to radome materials.     

New multifunctional porous Yb2SiO5 ceramics prepared by freeze casting

New porous Yb₂SiO₅ ceramics were prepared by a water-based freeze casting technique using synthesized Yb₂SiO₅ powders. The prepared porous Yb₂SiO₅ ceramics exhibit multiple pore structures, including lamellar channel pores and small pores, in its skeleton. The effects of the solid content and sintering temperature on the pore structure, porosity, dielectric and mechanical properties of the porous Yb₂SiO₅ ceramics were investigated. The sample with 20 vol% solids content prepared at 1550 °C exhibited an ultra-low linear shrinkage (i.e. 4.5%), a high porosity (i.e. 79.1%), a high compressive strength (i.e. 4.9 MPa), a low dielectric constant (i.e. 2.38) and low thermal conductivity (i.e. 0.168 W/(m K)). These results indicate that porous Yb₂SiO₅ ceramics are good candidates for ultra-high temperature broadband radome structures and thermal insulator materials.     

助烧剂和造孔剂对真空烧结SiC多孔陶瓷性能的影响

以粒度≤0.063mm的SiC为主要原料,分别加入30%(质量分数)的Al2O3-Y2O3与10%的Al2O3-高岭土复合助烧剂,并外加不同量(分别为12.8%、26.3%、30.0%和36.4%)的造孔剂羧甲基纤维素钠(CMC),制样后首先在空气炉中经过300℃2h或1100℃4h的预烧,然后在真空炉中于1550℃4h真空烧结而制备成SiC多孔陶瓷,并研究了助烧剂种类以及造孔剂CMC外加量对SiC多孔陶瓷显微组织、显气孔率及抗折强度的影响。结果显示:采用Al2O3-Y2O3作为助烧剂的SiC多孔陶瓷比Al2O3-高岭土作助烧剂的具有较高的抗折强度,显气孔率稍有减小;随着羧甲基纤维素钠量的增加,加入两种助烧剂的SiC多孔陶瓷均表现为显气孔率增加,抗折强度降低。