Structural,dielectric and ferroelectric properties of lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 ceramics prepared by Plasma Activated Sintering

Lead-free Ba_0.85Ca_0.15Zr_0.10Ti_0.90O₃ (BCZT) ceramics were prepared by Plasma Activated Sintering (PAS). The influence of PAS sintering temperature on the crystalline phase, microstructure, and, dielectric and ferroelectric properties of BCZT ceramics were studied. The phase structure of BCZT ceramics first changed from rhombohedral phase to the coexistence of rhombohedral and tetragonal phases and then to tetragonal phase as the sintering temperature increased. Microstructural characterization of BCZT ceramics indicated that PAS can obtain a compact microstructure at lower temperatures of 1150–1300 °C compared with that from common pressureless sintering. The BCZT ceramics showed different degrees of diffuseness with increased temperature, and the diffuseness exponents C are all approximately on the order of 10⁵ °C. The dielectric and ferroelectric properties of BCZT ceramics were enhanced with increased sintering temperature. BCZT ceramics sintered at 1250 °C exhibited optimum properties of room-temperature ε_r=2863, ε_m=6650, and 2P_r=25.24 μC/cm², resulting from the relatively higher tetragonal phase content of the MPB between tetragonal and rhombohedral phases together with a compact microstructure.     

Phase formation,electrical properties and morphotropic phase boundary of 0.95Pb(ZrxTi1−x)O3–0.05Pb(Mn1/3Nb2/3)O3 ceramics

Ferroelectric ceramics in specific composition of 0.95Pb(Zr_xTi_1?x)O₃–0.05Pb(Mn_1/3Nb_2/3)O₃ or PZT–PMnN (with x=0.46, 0.48, 0.50, 0.52, and 0.54) have been investigated in order to identify the morphotropic phase boundary (MPB) composition. The effects of Zr/Ti ratio on phase formation, dielectric and ferroelectric properties of the specimens have also been investigated and discussed. X-ray diffraction patterns indicate that the MPB of the tetragonal and rhombohedral phase lies in x=0.52. The crystal structure of PZT–PMnN appeared to change gradually from tetragonal to rhombohedral phase with increasing Zr content. The dielectric and ferroelectric properties measurements also show a maximum value (ε_r, tan δ and P_r) at Zr/Ti=52/48, while the transition temperature decreases with increasing Zr content.     

Structure,electrical, and thermal expansion properties of PZnTe–PZT ternary system piezoelectric ceramics

xPb(Zn_0.5Te_0.5)O₃–(1?x)Pb(Zr_0.5Ti_0.5)O₃ (PZnTe–PZT) ceramics were prepared by the solid‐state reaction method. The phase structure, microstructure, ferroelectric and dielectric properties and thermal expansion properties were systematically investigated. X‐ray diffraction analysis showed the morphotropic phase boundary (MPB) existed at the composition of x = 0.08, which was the coexistence of the rhombohedral phase and the tetragonal phase. The grain size of ceramics decreased rapidly from 10‐20 μm to 1‐3 μm when the PZnTe was added in. The PZnTe–PZT ceramics at the MPB composition showed the largest high field effective piezoelectric coefficient and the lowest strain hysteresis H. The dielectric permittivity and phase transition temperature exhibited strongly compositional dependence. A good linear relation was shown in T_m temperature vs x content and a DPT behavior was found in xPZnTe–(1?x)PZT (x = 0.02‐0.08). The thermal expansion properties showed a low thermal expansion coefficient in the low temperature while a high thermal expansion coefficient in the high temperature. Besides, the thermal expansion curve also showed the characteristic of DPT in PZnTe–PZT ceramics.     

Synthesis,structure and dielectric properties of (1−x)[0.9BiFeO3–0.1DyFeO3]–xPbTiO3 pseudo-binary ceramics

In order to develop multiferroics with large magnetization and polarization, we have prepared a series of (1?x)[0.9BiFeO₃–0.1DyFeO₃]–xPbTiO₃ [BDF–xPT] solid solution ceramics by solid state reaction. X-ray diffraction reveals that, with the increase of PbTiO₃ concentration, the solid solution transforms from a rhombohedral to a tetragonal phase with the presence of a morphotropic phase boundary (MPB) region located at 0.28≤x≤0.40 at room temperature, in which the rhombohedral, tetragonal and orthorhombic phases coexist. The temperature dependence of the dielectric permittivity indicates that the Curie temperature decreases with the increasing amount of PbTiO₃. Based upon the structural analysis and dielectric characterization, a preliminary phase diagram for the BDF?xPT pseudo-binary system has been proposed. It is found that the ceramics of compositions around the MPB exhibits much better dielectric properties with dielectric constant of the BDF–0.37PT ceramics reaching 459 at 1 kHz, confirming the beneficial effects of the MPB on the dielectric performance.     

Domain Structure Evolutions During the Poling Process for [011]‐Oriented PMN–xPT Crystals Across the MPB Region

The poling effect on the [011]‐oriented (1?x)Pb(Mg_1/3Nb_2/3)O₃‐xPbTiO₃ (PMN–xPT) single crystals across the morphotropic phase boundary (MPB) was studied. The dielectric and piezoelectric properties were investigated as a function of the poling field. Domain structure evolutions during the poling process were recorded. In the unpoled PMN–xPT phase diagram, an apparent rhombohedral (R)‐tetragonal (T) phase boundary exists. With room‐temperature poling, the structure transformation sequence strongly depends on the composition. The crystal experiences a direct transition to the 2R/2T domain state in the rhombohedral or tetragonal phase field beyond the MPB region, whereas within the MPB zone it is hard to achieve the 2R/2T engineered configuration although the initial state is either rhombohedral or tetragonal as well. The piezoelectric responses of the MPB·PMN–xPTs are extraordinary weak (d₃₃ ~ 250 pC/N), in contrast to the [011]‐oriented multidomain PMN–xPTs with ultrahigh‐piezoelectric coefficient (d₃₃ > 1000 pC/N). We demonstrate that a slight composition variation near the MPB will significantly influence the domain evolution route and piezoelectricity for the [011]‐oriented PMN–xPT crystals. We also confirm the feasibility to realize the 2R/2T engineered domain configuration for the [011]‐oriented MPB crystals, which will extend the desired portion of the Bridgeman‐grown boules with optimal piezoelectric properties.     

Temperature dependence of field‐responsive mechanisms in lead zirconate titanate

An electric field loading stage was designed for use in a laboratory diffractometer that enables in situ investigations of the temperature dependence in the field response mechanisms of ferroelectric materials. The stage was demonstrated by measuring PbZr_1?xTi_xO₃ (PZT) based materials—a commercially available PZT and a 1% Nb‐doped PbZr_0.56Ti_0.44O₃ (PZT 56/44)—over a temperature range of 25°C to 250°C. The degree of non‐180° domain alignment (η₀₀₂) of the PZT as a function of temperature was quantified. η₀₀₂ of the commercially available PZT increases exponentially with temperature, and was analyzed as a thermally activated process as described by the Arrhenius law. The activation energy for thermally activated domain wall depinning process in PZT was found to be 0.47 eV. Additionally, a field‐induced rhombohedral to tetragonal phase transition was observed 5°C below the rhombohedral‐tetragonal transition in PZT 56/44 ceramic. The field‐induced tetragonal phase fraction was increased 41.8% after electrical cycling. A large amount of domain switching (η₀₀₂=0.45 at 1.75 kV/mm) was observed in the induced tetragonal phase.     

PZT thick films on LTCC substrates with an interposed alumina barrier layer

PZT thick films (PbZr_0.53Ti_0.47O₃ with the addition of 6% PbO and 2% Pb₅Ge₃O₁₁) with a low sintering temperature were printed and fired on LTCC substrates (951, Du Pont), covered with an alumina barrier layer. The electrical characteristics (remanent polarisation, coercive field, dielectric constant and dielectric loss) of these PZT thick films, together with sets prepared on “unprotected” LTCC substrates and on alumina substrates were compared. Whereas the electrical characteristics of the films on LTCC substrates deteriorated significantly due to interactions between the LTCC substrates and the PZT layers the values obtained for the LTCC/alumina barrier structures were comparable with those on ceramic alumina substrates.     

Thermal Behaviors and Phase Evolution of Lead Zirconate Titanate Prepared by Sol–Gel Processing: The Role of the Pyrolysis Time before Calcination

Lead zirconate titanate (PZT) (53/47) powders were fabricated by the alkoxide-based sol–gel process, and the different drying times (1 and 12 h) at the pyrolysis temperature (300°C) of lead acetate were studied. The different pyrolysis time before calcination affects the onset and the violently dominant decomposition temperatures of lead acetate. According to the estimated activation energy results, the 1 h pyrolysis time showed that the transformation of the pyrochlore to perovskite phase is nucleation-controlled (424.5 kJ/mol), but the 12 h pyrolysis time is growth-controlled (125 kJ/mol). It was also found that the relative PZT perovskite contents were controlled by the carbonaceous material contents within the dried gels and the release rate of hydrocarbon during the pyrolysis process. With the proper pyrolysis-treated PZT powders, the dense, phase-coexisted PZT bulks could be produced at a low sintering temperature of 950° and 1000°C. The phase transformation of the PZT ceramics changed from the rhombohedral phase (900°C) to rhombohedral and tetragonal phase coexistence (950° and 1000°C), then finally to the monolithic tetragonal phase (1050° and 1100°C). A phase diagram is plotted based on the different sintering conditions. The dielectric properties were dependent on the relative densities of the PZT bulks, and the PZT bulks sintered at 1000°C for 6 h had superior dielectric constant (1080) and lowest dielectric loss (0.7%).     

Sintering Behavior,Properties, and Applications of Co‐Fired Piezoelectric/Low Temperature Co‐Fired Ceramic (PZT‐SKN/LTCC) Multilayer Ceramics

Materials and processing conditions have been developed allowing co‐firing of fluxed PZT‐SKN materials with commercial low temperature co‐fired ceramic (LTCC) tapes. Previously, Pb(Zr_0.53, Ti_0.47)O₃–Sr(K_0.25, Nb_0.75)O₃ (PZT‐SKN) ceramics fluxed with 1 wt% LiBiO₂ and 1 wt% CuO addition were shown to sinter to high density at 900°C for 1 h, with a large d₃₃ piezoelectric coefficient of ~415 pm/V. Currently, the master sintering curve (MSC) approach has been used to study the densification behaviors of fluxed PZT‐SKN and LTCC tapes. Different sintering mechanisms for fluxed PZT‐SKN ceramics and LTCC materials are confirmed by analyzing the apparent activation energy (Q_a). Using knowledge gained from MSC results, an optimized sintering profile was developed. Multilayer PZT‐SKN/HL2000 (HeraLock^? Tape, Heraeus) stacks co‐fired at 900°C for 0.5 h maintain large piezoelectric coefficient (high field d₃₃ > 340 pm/V). EDS analysis reveal limited interdiffusion of Pb from PZT‐SKN layers in LTCC and the appearance of Al, Ca, and Si in the PZT‐SKN near the PZT‐SKN/LTCC interface. Further, elemental interdiffusion was not detected at the center of piezoelectric layer in PZT‐SKN/LTCC multilayer ceramics and no subsequent reduction in piezoelectric coefficient d₃₃ was observed. Finally, a piezoelectric microbalance with mass sensitivity of 150 kHz/mg was fabricated using the materials and methods developed.     

Structure,Microwave Dielectric Properties,and Novel Low‐Temperature Sintering of xSrTiO3–(1−x)LaAlO3 Ceramics with LTCC Application

xSrTiO₃–(1?x)LaAlO₃ ceramics with ZnO–B₂O₃ sintering aid were prepared by solid‐state reaction method leading to a significant decrease in sintering temperature from 1550°C to 1050°C. The structure, microwave dielectric properties, and low‐temperature sintering behavior were systematically investigated. The results revealed the relationships among ionic size, ionic polarizability and cell volume. With increasing additive, chemical ordering of B‐site cations was indicated with selected area electron diffraction (SAED) patterns, HRTEM images and Raman spectrum, which contributed to the greatly enhanced microwave dielectric properties. Particularly, the 0.7Sr_0.85 Mg_0.15TiO₃–0.3LaAlO₃ ceramics modified with 10 wt % ZnO‐B₂O₃ can further decrease the sintering temperature down to 950°C without deteriorating its performance. Thermal tests implied ceramics featured good chemical compatibility with Cu/Ag electrode. Thus, they can be cofired with internal Cu/Ag electrodes in special patterns to fulfill different electrical functions for LTCC (low‐temperature cofired ceramic) application.     

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.     

ZnO-B2O3玻璃对Li2Zn3Ti4O12-CaTiO3复合陶瓷低温烧结及性能的影响

采用传统固相反应法制备0.94Li₂Zn₃Ti₄O₁₂-0.06CaTiO₃(LZT-CT)复合陶瓷,采用高温熔融法制备ZnO-B₂O₃(ZB)玻璃;以ZB玻璃为烧结助剂,研究了添加不同质量分数(x=0.5%、1.0%、1.5%、2.0%和2.5%)的ZB玻璃对LZT-CT复合陶瓷的烧结特性、物相组成、微观结构以及微波介电性能的影响。结果表明:ZB玻璃能有效地将LZT-CT复合陶瓷的烧结温度从1 175 ℃降低到875 ℃,并促进了LZT-CT复合陶瓷的致密化。当ZB玻璃掺量x≤2.5%时,LZT-CT复合陶瓷中除了LZT、CT相,没有出现其他新相。随着ZB玻璃添加量增加,复合陶瓷的体积密度、介电常数(ε_r)、品质因数(Q×f)均先增加后减小,谐振频率温度系数(τ_f)变化不大,在(-2.25~4.51)×10^-6/℃波动。当ZB玻璃掺量为2.0%时,LZT-CT复合陶瓷在875 ℃烧结2 h,获得最大体积密度(4.22 g/cm³)以及优异的微波介电性能,ε_r=23.9,Q×f=58 595 GHz,τ_f=-0.14×10^-6/℃。     

Structural Evolution and Properties of 0.3Pb(In1/2Nb1/2)O3–0.38Pb(Mg1/3Nb2/3)O3–0.32PbTiO3 Ferroelectric Ceramics with Different Sintering Times

The structural evolution and properties of 0.3Pb(In_1/2Nb_1/2)O₃–0.38Pb(Mg_1/3Nb_2/3)O₃–0.32PbTiO₃ (0.3PIN‐0.38PMN‐0.32PT) ferroelectric ceramics with different sintering times have been investigated. The content of the tetragonal phase is increased in samples sintered for more than 6 h, despite that the composition falls in the rhombohedral region of the previously established phase diagram. The results show that the metastable tetragonal phase at room temperature is induced and stabilized by the tensile residual stresses. Excessively long sintering time generally leads to grain coarsening, loss of lead, and deterioration of properties, while the increasing amount of the tetragonal phase, and the large residual tensile stress appear to improve the dielectric and electromechanical properties. This study offers new insights into the sintering of Pb‐based ferroelectric ceramics with complex compositions.     

Phase coexistence region and dielectric properties of PZT ceramics

In PZT ceramics it is commonly observed that the tetragonal and the rhombohedral phases may coexist around the morphotropic phase boundary (MPB). Some controversy still exists concerning the causes of the real occurrence of the phase coexistence, the distribution of the coexisting phases and their chemical and structural properties. In a previous work we found a relation between the width of the coexistence region and the grain size of the ceramic that could be explained by the statistical distribution model, as long as the elementary phase volumes were considered as the ferroelectric domains inside the grain. In the present work the structural parameters of the phases and the dielectric permittivity of PZT in a compositional range covering the phase coexistence region are determined and analysed. It is observed that in both tetragonal and rhombohedral phases the permittivity increases as the lattice distortion relative to the cubic symmetry decreases. The dielectric permittivities of PZT inside the phase coexistence region were calculated considering that the phase coexistence corresponds to a statistical distribution of phases with the same composition. This model provides dielectric results consistent with the experimental ones. It was also shown that the maximum of the dielectric properties in the MPB does not result from the phase coexistence, but it is a consequence of the approach to a minimum structure distortion.     

Effect of particle size on the optical properties of lead zirconate titanate nanopowders

Nanopowder samples of lead zirconate titanate (Pb_1.1Zr_0.52Ti_0.48O₃ or PZT) were prepared by the sol‐gel method with controlled pH values. The samples were characterized using FTIR spectroscopy, XRD, FE‐SEM, and TEM techniques. Most of the peaks in the XRD pattern were related to the coexistence of tetragonal‐rhombohedral phases and confirmed the formation of PZT with a perovskite structure. Also, the crystallite size of PZT nanopowders was in a range of 17‐28 nm. FTIR spectroscopy revealed a longitudinal optical (LO) and transverse optical (TO) phonon modes corresponding to the stretching vibration of Ti‐O and Zr‐O bonds. The influence of pH values on the LO and TO phonon modes, LO‐TO splitting, refractive index n(ω), extinction coefficient k(ω), and the real ?₁(ω) and imaginary ?₂(ω) parts of dielectric function was discussed. These properties were investigated in the mid‐infrared region (450‐750 cm^?1). The energy loss function Im[?1/(?)] of PZT nanopowders was obtained by Kramers‐Kronig dispersion relations. The TO phonon frequency decreases with increasing crystallite size of the PZT samples. This effect does not happen at pH 8 to pH 9. As the crystallite size increased from 17.26 nm (at pH 5) to 27.25 nm (at pH 7), the LO‐TO splitting increased as well. This result showed that the optimum pH for absorption of IR radiation and optical application was at pH 7.     

Thermodynamics of Ferroelectric Solid Solutions with Morphotropic Phase Boundaries

A thermodynamic analysis is presented for the diffusionless phase diagrams of ferroelectric solid solutions that display a morphotropic phase boundary (MPB) separating adjacent tetragonal and rhombohedral phases. Equations are developed for the shape of the MPB, the locations of triple and tricritical points, and for the line along which the anisotropy of polarization vanishes. The appearance of lower symmetry orthorhombic and monoclinic phases is considered and the topologies of energy surfaces in the region of the phase diagram where these phases may stabilize are illustrated. The theory is applied to the solid solution of lead zirconate with lead titanate (PZT) and relationships between polar anisotropy and the transformation strain, dielectric susceptibility and piezoelectric properties, are discussed. The analysis is used to reproduce phase boundary lines for solid solutions of lead titanate with lead magnesium niobate (PMN‐PT) and lead zinc niobate (PZN‐PT) and composition–temperature diagrams along isopleths in the ternary system PMN‐PZT are estimated. The anisotropies of polarization in solid solutions based on lead titanate and barium titanate are contrasted. The results provide a thermodynamic framework useful for guiding experimental investigations of ferroelectric solid solutions and for generating energy functions used in constitutive modeling and phase field simulations of microstructure and properties.     

Effects of thermal strain on electric properties of lead zirconate titanate thin films upon LaNiO3 coated base metal plates

Electric properties for ferroelectric lead zirconate titanate (PZT50/50, 45/55, 40/60, 30/70) thin films on base metal plates with different thermal expansion coefficient (TEC) were calculated by a phenomenological model. Results show that when the TEC of substrates increases, dielectric constant, tunability and piezoelectric coefficient d₃₃ of all PZT thin films with tetragonal phase are decreased due to the larger compressive thermal strain. PZT50/50 thin films deposited on smaller TEC substrates can achieve higher dielectric constant, tunability and d₃₃. The computed dielectric constant of PZT50/50 thin films is in accordance with the measured results from sol-gel experimental process, and the trend of dielectric constant of PZT films adjacent to morphotropic phase boundary (MPB) derived from some references also agrees with that from calculation. These results suggest that higher tunability and d₃₃ of PZT films can be obtained by choosing smaller TEC substrates.     

Influence of barium borosilicate glass on microstructure and dielectric properties of (Ba,Ca)(Zr,Ti)O3 ceramics

Barium borosilicate (BBS) glass was added as a sintering aid to (Ba_0.7Ca_0.3)TiO₃-Ba(Ti_0.8Zr_0.2)O₃ (BCZT) ceramics at levels from 2 to 15?wt%, yielding enhanced densification. The addition of BBS also induced changes in phase composition, from predominantly tetragonal to orthorhombic at room temperature. It is shown that the changes in phase content are caused by a shift of the orthorhombic to tetragonal phase transformation from below room temperature to ≈50?°C. An additional high temperature transition around 120?°C was also identified. These observations are interpreted in terms of the development of chemical heterogeneity associated with the redistribution of dopant elements (particularly Zr and Ca) through the liquid phase during sintering. The relative permittivity and electric field-induced polarisation values were generally degraded by the presence of the glass phase, but a reduction in ferroelectric hysteresis and improved densification behaviour have potential benefits in dielectric energy storage applications.     

Mechanical,thermal, and dielectric properties of glass mullite composites for low-temperature cofired ceramic and radome applications

SiO₂-Al₂O₃-CaO-based glass (10–60 wt%)/mullite composites were investigated for the LTCC and radome applications. The optimum densification temperatures decreased from 1550°C (10 wt% glass) to 1400°C (30 wt% glass) by means of liquid-phase sintering, and to 850°C–825°C (50–60 wt% glass) by means of viscous phase sintering. XRD analysis showed that mullite was the main phase as well as in situ crystallized anorthite after 825°C. The composite with 20 wt% glass was a suitable candidate for the radome applications (bulk density = 2.86 g/cm³ after sintering at 1450°C, dielectric constant (loss) = 7.12 (0.0025) at 5 MHz, thermal expansion coefficient = 4.27 ppm/°C between 25°C and 800°C, thermal shock resistance parameter = 162°C), and the composite with 50 wt% glass was a suitable candidate for the low-temperature cofired ceramic applications (bulk density = 2.64 g/cm³ after sintering at 850°C, dielectric constant (loss) = 6.79 (0.0043) at 5 MHz, thermal conductivity = 2.11 W/m⋅K at 25°C, and thermal expansion coefficient = 3.93 ppm/°C between 25°C and 300°C).     

Complex structural contribution of the morphotropic phase boundary in Na0.5Bi0.5TiO3 - CaTiO3 system

The correlation between structure and dielectric properties of lead-free (1-x)Na_0.5Bi_0.5TiO₃ - xCaTiO₃ ((1-x)NBT - xCT) polycrystalline ceramics was investigated systematically by X-ray diffraction, combined with impedance spectroscopy for dielectric characterizations. The system shows high miscibility in the entire composition range. A morphotropic phase boundary (MPB), at 0.09?≤?x?<?0.15 was identified where rhombohedral and orthorhombic symmetries coexist at room temperature. The fraction of orthorhombic phase increases gradually with x in the MPB region. Dielectric measurements reveal that the relative permittivity increase with addition of Ca²⁺. This behavior is unusual with this kind of doping. A thermal hysteresis occurred only in the MPB composition which varies in a non-monotonically manner with x, detected by dielectric properties. This phenomenon is related to the crystalline microstructure by a linear relationship between the fraction of each phase and dielectric properties, and, more precisely, to the strong interaction between rhombohedral and orthorhombic phases.