Structural origin of size effect on piezoelectric performance of Pb(Zr,Ti)O3

Grain size effect plays a vital role in piezoelectric performance from both scientific and technological view. However, the underlying structural mechanism related to grain size is still unclear. In the present study, the structural mechanism of grain size effect on piezoelectric performance has been revealed in the prototype Pb(Zr,Ti)O₃ system by using in-situ synchrotron X-ray diffraction. The miniaturization of grain size tends to favor the appearance of higher symmetric tetragonal phase, while a single monoclinic phase is determined in the coarse-grained ceramics. The direct structural evidence reveals that both tetragonal and monoclinic phases in the fine-grained ceramics are less sensitive to the electric field, corresponding to the inferior piezoelectric performance, while the single monoclinic phase in the coarse-grained ceramics is more active to be driven by the electric field, generating good piezoelectric behavior. Both domain switching ability and lattice strain are suppressed with decreasing grain size, which directly leads to the deterioration in piezoelectric performance. The current results will benefit the structural understanding of the size effect of piezoelectric and other related systems.     

Effects of addition of Pb(Y1/2Nb1/2)O3 (PYN) on microstructure and piezoelectric properties of Pb(Zr0.53Ti0.47)O3

Pure and Pb(Y_1/2Nb_1/2)O₃ (PYN)-doped Pb(Zr_0.53Ti_0.47)O₃ have been characterized. The samples were prepared by conventional mixed-oxide ceramic technology. PYN dopant was added to PZT at content levels ranging from 1 to 2.5 mol%. The microstructures of the samples were examined using SEM and TEM. The average grain size was observed to decrease as the dopant content increased. Herringbone-like and wedge-shaped domain patterns were observed in all the samples. The piezoelectric properties of PZT were greatly improved by the addition of PYN. The highest piezoelectric constant d₃₁ was nearly twice that of pure PZT.     

Pb(Zr0.53Ti0.47)O3陶瓷超细粉体制备及分散研究

用化学共沉淀法合成了陶瓷Pb(Zr0.53Ti0.47)O3超细粉体,以聚乙二醇(PEG)为分散剂对所得粉体进行分散。通过X衍射、扫描电镜分析,研究了合成条件和煅烧温度对PZT粉体性能的影响。结果表明,随着煅烧温度的升高,PZT超细粉晶化度提高,一次晶粒尺寸增加,而二次粒子尺寸却减小。当分散剂分子量为10000,用量为1%时,得到分散良好的超细粉体。测定了用合成的粉体烧结的PZT陶瓷的压电性能。     

Effects of LiF addition on microstructure and dielectric properties of CaCu3Ti4O12 ceramics

The effects of small amounts of lithium fluoride sintering aid on the microstructure and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated. CCTO polycrystalline ceramics with 0.5 and 1.0 mol% LiF, and without additive were prepared by solid state synthesis. Good densification (>90% of the theoretical density) was obtained for all prepared materials. Specimens without the sintering aid and sintered at 1090 °C exhibit secondary phases as an outcome of the decomposition reaction. The mean grain size is controlled by the amount of LiF in specimens containing the additive. Impedance spectroscopy measurements on CaCu₃Ti₄O₁₂ ceramics evidence the electrically heterogeneous nature of this material consisting of semiconductor grains along with insulating grain boundaries. The activation energy for grain boundary conduction is lower for specimens prepared with the additive, and the electric permittivity reached 53,000 for 0.5 mol% LiF containing CCTO.     

Effect of Samarium substitution on dielectric properties of (Pb)(Zr, Ti, Fe, Nb)O3 type ceramic system

The influence of Samarium substitution on the dielectric properties of modified PZT composition with representative formula [Pb_1−xSm_xZr_0.588Ti_0.392Fe_0.01Nb_0.01O₃] system is reported. Samarium (Sm) was varied from 0 to 0.01/FU in the present system in a step of 0.0025. The samples were prepared by the traditional solid state reaction process. XRD analysis showed all the samples to be single phase with tetragonal structure. Dielectric properties were studied in detail as a function of frequency and temperature (from room temperature (RT) 30 to 400 °C). All compositions show phase transition and the transition temperature (T_C) is found to decrease with increase in Sm substitution. Room temperature dielectric constant shows an increasing trend while loss improves with Sm doping.     

Piezoelectric properties of (1-x)BZT-xBCT system for energy harvesting applications

In this study, we investigated (1-x)Ba(Zr_0.2Ti_0.8)O₃–x(Ba_0.7Ca_0.3)TiO₃ lead-free piezoelectric ceramics for energy harvester applications. The (1-x)BZT-xBCT ceramic is a promising lead-free piezoelectric material in the field of piezoelectric energy harvesting. Piezoelectric and energy properties of (1-x)BZT-xBCT ceramics were analyzed to confirm the possibility of using them as energy-harvesting materials. Especially, the vicinity of the phase convergence region was investigated to improve their piezoelectric properties. In the phase convergence region, cubic, rhombohedral, orthorhombic, and tetragonal regions co-exist within the narrow region. Near the phase transition region between the orthorhombic and tetragonal phase, the highest piezoelectric property d₃₃?=?464 pC/N and the highest energy density of 158.5 μJ/cm³ were observed. This output energy density of 158.5 μJ/cm³ is the recorded highest value among lead-free ceramics. We found that the optimal sintering temperature was 1475?°C and the optimal composition was BZT-0.5BCT.     

Microstructure and electric properties of Pr-doped Pb(Zr0.52Ti0.48)O3 ceramics

Improving the piezoelectric activity of lead zirconate titanate (PZT) ceramics is of great importance for practical applications. In this study, the influence of Pr³⁺ doping on the ferroelectric phase composition, microstructure, and electric properties on the A-site of (Pb_1-1.5xPr_x)(Zr_0.52Ti_0.48)O₃ is extensively investigated. A dense and fine microstructural sample is obtained with the introduction of Pr³⁺. The results show that the morphotropic phase boundary (MPB) moves to the rhombohedral phase region. The rhombohedral and tetragonal phases exhibit an ideal coexistence in the 4 mol.% Pr³⁺ doped (PPZT4) samples. Lead vacancy and the reduction of the potential energy barrier are considered to be the key mechanisms for donor doping, which is upheld by the Pr³⁺ doping. Combining the I-E hysteresis loops with the P-E hysteresis loops, it becomes apparent that both contribution maximums of the domain switching and residual polarisation are in PPZT4. Moreover, the thermal aging resistance of PZT is improved by doping, and the temperature stability is optimised from 83% in PZT to 96% in PPZT4. Hence, an appropriate amount of Pr³⁺ doping can effectively improve the piezoelectric activity of PZT ceramics in the MPB area and optimise the performance stability of the material under application temperatures.     

Structure of Duplex Multilayer Pb(Zr0.53Ti0.47)O3> Films Prepared by Sol-Gel Processing

Multilayer PZT films were prepared by sol-gel processing, and their structure and composition were investigated by cross-sectional TEM and EDX analyses. The films made by firing at 600°C (as-deposited films) are composed of alternating porous and dense layers, and the porosity increases by a factor of 2 through heating at 750°C. The pyrochlore phase observed in the as-deposited films turns to the perovskite phase by the heat treatment at 750°C. The Ti/Zr ratio along the film stacking direction is shown to change with the elevation of heat treatment temperature. The porous soft layers are considered to reduce the thermal stress and prevent the introduction of cracks during the firing process.     

Structure and electrical properties of Ca2+-doped (Na0.47Bi0.47Ba0.06)TiO3 lead-free piezoelectric ceramics

The lead-free piezoelectric ceramics (Na_.47Bi_.47Ba_.06)_1-xCa_xTiO₃ (x?=?0, 0.01, 0.02, 0.03, 0.05, and 0.08, abbreviated as BNBTC/0, BNBTC/1, BNBTC/2, BNBTC/3, BNBTC/5, and BNBTC/8, respectively) were obtained using the solid-state reaction method. The structure, electric conductivity, and dielectric, ferroelectric, and piezoelectric properties of the Ca²⁺-doped (Na_.47Bi_.47Ba_.06)TiO₃ ceramics were thoroughly investigated. The ceramics sintered at 1200?°C exhibit dense microstructures, having relative densities higher than 96%. The X-ray diffraction results demonstrate that all ceramics have a pure perovskite structure. The mean grain sizes of the ceramics are related to the Ca²⁺ quantity. A small quantity of Ca²⁺ ions (x?≤?0.03) improves the piezoelectric and ferroelectric properties of the samples. The dielectric behavior of the samples is sensitive to the Ca²⁺ content and electric poling. The results demonstrate that the electrical properties of the (Na_.47Bi_.47Ba_.06)TiO₃ lead-free ceramics can be well tuned by varying the Ca²⁺ quantity.     

Effect of 1 wt% LiF additive on the densification of nanocrystalline Y2O3 ceramics by spark plasma sintering

Densification of nanocrystalline cubic yttria (nc-Y₂O₃) powder, with 18 nm crystal size and 1 wt% LiF as a sintering additive was investigated. Specimens were fabricated by spark plasma sintering at 100 MPa, within the temperature range of 700-1500 °C. Sintering at 700 °C for 5 and 20 min resulted in 95% and 99.7% dense specimens, with an average grain size of 84 and 130 nm, respectively. nc-Y₂O₃ without additive was only 65% dense at 700 °C for 5 min. The presence of LiF at low sintering temperatures facilitated rapid densification by particle sliding and jamming release. Sintering at high temperatures resulted in segregation of LiF to the grain boundaries and its entrapment as globular phase within the fast growing Y₂O₃ grains. The sintering enhancement advantage of LiF was lost at high SPS temperatures.     

Investigation on the origin of the giant dielectric constant in CaCu3Ti4O12 ceramics through analyzing CaCu3Ti4O12-HfO2 composites

A full range of CaCu₃Ti₄O₁₂-HfO₂ (CCTO-HfO₂) composites were prepared by sintering mixtures of the two components at 1000 °C for 10 h. X-ray diffraction studies confirmed the two-phase nature of the composites. The evolution of the microstructure in the composites, in particular, the size distribution of CCTO grains, was examined by scanning electron microscopy. The studies showed that, as more HfO₂ was added, the abnormal grain growth of CCTO and coarsening of the microstructure were gradually suppressed. As a result, the average CCTO grain size was reduced from 50 to 1 μm. The measured dielectric constants agree well with the values calculated from Lichtenecker's logarithmic law, using only the dielectric constants of pure CCTO and HfO₂ as two end points. The agreement suggests to us that the dielectric constant of CCTO is dominated by domain boundaries within the grains rather than by grain boundaries between the grains.     

Influence of filler size and concentration on the low and high temperature dielectric response of poly(vinylidene fluoride) /Pb(Zr0.53Ti0.47)O3 composites

Poly(vinylidene fluoride)/Pb(Zr0.53Ti0.47)O3([PVDF]1 ? x/[PZT]x ) composites of volume fractions x and (0?C3) type connectivity were prepared in the form of thin films. The films were prepared by solvent casting with PZT powder of 0.84, 1.86, and 2.35???m average size with filler contents up to 40?% volume. The crystalline phase of the polymer matrix was the nonpolar ??-phase and the polar ??-phase. Dielectric measurements were performed in order to evaluate the influence of the filler size and content as well as the effect of the polymer matrix in the overall response of the material. No nucleation effect of any of the phases was observed for the used fillers. The spherulitic structure of the pure ??-PVDF and the characteristic porosity of the ??-phase material are destroyed for high PZT volume fractions. The inclusion of ceramic particles in the PVDF polymer matrix increases the complex dielectric constant of the composites independently of the PVDF polymer matrix. The dielectric properties of the composites are mainly affected by the amount of the ceramic particles. With respect to the relaxation processes of the polymer, the activation energy of the ??_a-relaxation increases and the glass transition temperature decreases with increasing particle size and content. The high-temperature conductivity decreases with increasing filler content and there is an important contribution of the Maxwell-Wagner-Sillars effect to the overall dielectric response.     

Size effect on dielectric properties of fine-grained BaTiO3 ceramics

The effect of grain size on the dielectric behavior of high-purity, fine-grained BaTiO₃ ceramic has been investigated. It was found that the dielectric constant and dissipation factor changed much with the decreasing of average grain size. The specimen with grain size of 280 nm had a high dielectric constant at room temperature, and the _r-T and tanδ-T curves remarkably changed with the grain size. Part of the grains remaining ferroelectric structure was ascribed to the high value of dielectric constant. ©     

Dielectric relaxation behavior and energy storage properties in Ba0.4Sr0.6Zr0.15Ti0.85O3 ceramics with glass additives

Ba_0.4Sr_0.6Zr_0.15Ti_0.85O₃ ceramics with SrO–B₂O₃–SiO₂ glass additives were prepared via the solid state reaction route. The effects of glass contents on the sintering behavior, dielectric properties, microstructures, and energy storage properties of BSZT ceramics were investigated. Dielectric breakdown strength of 22.4 kV/mm was achieved for BSZT ceramics with 20 wt% glass addition. Dielectric relaxation behavior was observed in dielectric loss versus temperature plots. In order to investigate the mechanism of dielectric breakdown performance, the relationship between dielectric breakdown strength and grain boundary barrier was studied by the measurements of breakdown strength and activation energy. A discharged energy density of 0.45 J/cm³ with an energy efficiency of 88.2% was achieved for BSZT ceramics with 5 wt% glass addition.     

Structural and electrical properties of Pb(Zr0.53Ti0.47)O3 films prepared on La0.5Sr0.5CoO3 coated Si substrates

PbZr_0.53Ti_0.47O₃ (PZT) thin films with thickness of 0.9 μm were prepared on La_0.5Sr_0.5CoO₃ (LSCO) coated Si substrates. Both PZT and LSCO were prepared by the sol–gel method. The concentration of LSCO sol was varied from 0.3 to 0.1 mol/L, which could modify the preferential orientation of PZT thin films and consequently affect the dielectric and ferroelectric properties. The LSCO electrode layers derived from lower sol concentration of 0.1 mol/L have much more densified structure, which facilitates the formation of (1 0 0) textured PZT films with smooth and compact columnar grains. PZT thin films prepared on the optimized LSCO films exhibit the enhanced dielectric constant and remnant polarization of 980 and 20 μC/cm², respectively.     

Normal sintering of (K, Na)NbO3-based lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics have received more attention due to the environmental protection of the earth. (K, Na)NbO₃-based ceramics are one of the most promising candidates. Normal sintering of un-doped and Li/Ta co-doped (K, Na)NbO₃ ceramics was investigated to clarify the optimal sintering condition for densification, microstructure and electrical properties. It was found that density increased greatly within a narrow temperature range but turned to decrease when the sintering temperature slightly exceeded the optimal one. Piezoelectric properties also showed similar relationship between the density and sintering temperature, but the highest piezoelectric strain coefficients were obtained at the temperatures lower than that for the highest density. The grain growth and property change as a function of sintering temperature were discussed on basis of the formation of liquid-phase and the composition deviation caused by the volatilization of alkali components during sintering.     

Temperature dependence of piezoelectric properties on Nd and V co-substituted Bi4Ti3O12 ceramics for ceramic resonator applications

The temperature dependences of the piezoelectric properties of (Bi_4−yNd_y)_1−(x/12)(Ti_3−xV_x)O₁₂ [BNTV-x, y (x = 0.01, y = 0.00–1.00)] were investigated for environmentally friendly lead-free piezoelectric ceramic resonators with low-temperature coefficients of resonance frequency, TC-f. The |TC-f| in the (33) mode improved with increasing concentration of modified Nd ions, y, and exhibited the smallest |TC-f| value of 77.4 ppm/°C at y = 0.75 (BNTV-0.75). The |TC-f| in the other vibration mode (t), was also investigated for the BNTV-0.75 ceramic, and a smaller value of 42 ppm/°C was obtained. The (t) mode of the BNTV-0.75 ceramic showed excellent piezoelectric properties: Q_m = 4200, Q_e max = 31 and TC-f = −49.8 ppm/°C. These properties are very similar to those of commercialized hard PZT ceramics for resonator applications. The BNTV-0.75 ceramic seems to be a superior candidate material for lead-free piezoelectric applications of ceramic resonators.     

Influence of Al2O3 addition on microstructure,defects level and magnetic properties of LiTiZn ferrite ceramics

In the present work, the results of the influence of diamagnetic additives on the defects level of ferrite ceramics, its microstructure and magnetic properties are presented. A method based on a mathematical analysis of the experimental temperature dependences of the initial permeability was used for estimation of the defects level in the samples. Model samples containing a controlled amount of the diamagnetic additive Al₂O₃ served to test the possibility of monitoring this method of nonmagnetic phases of ferrite ceramics. It was shown that with an increase in the concentration of the Al₂O₃ additive in the range of (0–0.5) wt%, a significant increase in the defects level was observed almost 6-fold. The data from SEM micrographs showed that the addition of Al₂O₃ affects the type of grains of ferrite ceramics, but does not affect their grain size. Grains are highly agglomerated and show large grain size dispersion and also pore. Obtained data were compared to hysteresis loop parameters. It is shown that with an increase in the concentration of the Al₂O₃ addition, there is a regular decrease in the residual induction and an increase in the coercive force. However, such changes in hysteresis loop parameters are small in comparison to defects level. Investigations of the true physical broadening of the diffraction reflections were performed for the same model samples in order to compare the change in the defects level to the direct X-ray diffraction measurements of micro deformations. The defects level as a characteristic of the elastic stress of a ferrite ceramics is proposed. This assumption follows from a linear relationship between the defects level and the width of the diffraction reflections. The consistency of the obtained results made it possible to evaluate the high efficiency and sensitivity of the method for defects level estimating.