Structure and properties of Bi(Zn½Ti½)O3-modified Pb(Zr,Ti)O3 piezo-/ferroelectric ceramics around the ternary morphotropic phase boundary

To develop high-performance piezo-/ferroelectric materials, Bi(Zn_½Ti_½)O₃–PbZrO₃–PbTiO₃ (BZT–PZ–PT) ternary solid solution with compositions around the morphotropic phase boundary (MPB) is synthesized by solid-state reaction. The crystal structure and electric properties are investigated systematically by X-ray powder diffraction (XRD), dielectric spectroscopy, and ferroelectric and piezoelectric measurements. On the basis of the results of the XRD, dielectric and ferroelectric measurements, the pseudo-binary phase diagram of the yBi(Zn_½Ti_½)O₃–(1 − y)[(1 − x)PbZrO₃–xPbTiO₃] system has been constructed for three series, namely, y = 0.05, 0.10, and 0.15. It is found that the introduction of BZT into the PZT system makes the paraelectric to ferroelectric phase transition more diffuse, brings the MPB to a lower PT content, and enlarges the MPB region. The best properties with an improved dielectric constant ε' = 1248, and a large remnant polarization P_r = 33 μC/cm², as well as a relatively high T_C = 286°C, and a high coercive field E_c = 23 kV/cm was achieved in the y = 0.15 series with MPB composition x = 0.425, making it a promising material for high-power piezoelectric applications.     

High electric field-induced strain properties in La-doped Pb(In1/2Nb1/2)O3–PbZrO3–PbTiO3 relaxor ferroelectric ceramics

Piezoelectric ceramics with high strain response and low hysteresis are highly in demand for high-performance actuator applications. Unfortunately, the trade-off relationship between large field-induced strain and low hysteresis in piezoelectric ceramics is a key challenge for designing high-performance piezoelectric actuators. Herein, ymol%La-doped 0.10 Pb(In_1/2Nb_1/2)O₃-xPbZrO₃-(0.90–x)PbTiO₃ [0.10PIN-xPZ-(0.90-x)PT: ymol%La] ternary relaxor ferroelectric ceramics were prepared by conventional solid-state reaction technique. Pb(In_1/2Nb_1/2)O₃ (PIN) as a relaxor end member was introduced into (Pb,La) (Zr,Ti)O₃ (PLZT) system to improve relaxor characteristics and strain properties. A giant strain of 0.23% was obtained in 0.10PIN-0.59PZ-0.31 PT: 8mol%La ceramic at the electric field of 20 kV/cm, with a high piezoelectric d₃₃* of 1150 pm/V and low hysteresis H_y of 6.4%, exhibiting a potential application in high-performance piezoelectric actuators. Furthermore, the effects of La ion doping and components on the ferroelectric, dielectric and electric field-induced strain properties were investigated, and provides a new way for improve the strain properties of piezoelectric materials.     

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.     

Densification behavior and electrical properties of CuO-doped Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 ternary ceramics

CuO modified Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PMN–PT) ternary relaxor based ferroelectrics with the composition near the morphotropic phase boundary were synthesized by two-step columbite precursor method. The introduction of CuO significantly improved the sinterability of PIN–PMN–PT ceramics, resulting in the full densification of samples at lower sintering temperatures. It also profoundly modified the crystal structure and fracture mode of the ceramics. Properly increasing CuO content led to the disappearance of rhombohedral-tetragonal phase transition, remarkably improved the Curie temperature (T_c), and made the ceramics more relaxorlike. The ternary ceramics doped with 0.25 wt% CuO possessed optimum piezoelectric properties (d₃₃=584 pC/N, d₃₃^*=948 pC/N, and k_p=0.68), high ferroelectric properties (E_c=9.9 kV/cm, and P_r=33.1 μC/cm²), low dielectric loss (tan δ=0.9%), and wider temperature usage range (T_c=225 °C). The obtained properties are much higher than those of previously reported PIN–PMN–PT based ceramics, indicating that CuO doped PIN–PMN–PT is a promising candidate for electromechanical applications with high performance and wide temperature/electric field usage ranges.     

Optimisation of matrix composition for texturing of morphotropic phase boundary Pb(Mg1/3Nb2/3)O3–PbZrO3–PbTiO3 piezoelectric ceramics using BaTiO3 template

Texturing is an innovative method for fabricating high-performance piezoelectric ceramics. However, the optimal conditions for successful texturing must be evaluated to obtain high performance. Herein, the texturing behaviour of Pb(Mg_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ (PMN–PZ–PT) piezoelectric ceramics using plate-like BaTiO₃ crystals as a template was found to be strongly dependent on the chemical composition of the matrix. Given that the solubility of BaTiO₃ in the matrix increased with the PZ content, an excessive amount (>20 mol%) of the BaTiO₃ template was necessary for texturing a 0.2PMN–0.38PZ–0.42PT, while 3 mol% of the BaTiO₃ template could texture a 0.4PMN–0.22PZ–0.38PT. Owing to well-aligned textured grains and the complete consumption of randomly oriented matrix particles, a textured 0.4PMN–0.22PZ–0.38PT sample prepared by tape-casting under optimised conditions yielded a Lotgering factor of 97 % and an induced strain of 0.2 % with an electric field of 2 kV/mm.     

Domain structure and evolution in ZnO-modified Pb(Mg1/3Nb2/3)O3–0.32PbTiO3 ceramics

The doping of ZnO is efficient to improve the piezoelectric property and thermal stability of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT) based ceramics. However, the underlying physics, especially the local domain structures of the ZnO modified PMN–PT ceramics, which is strongly associated with the electric properties, is not clear yet. In this paper, we investigated the local domain structures and their evolution as a function of x in PMN–0.32PT:xZnO ceramics. It was found that, the domain evolution is mainly caused by the growth of grain size induced by the sintering aiding effect of ZnO at x < 0.04, and the domain evolution can be attributed to the phase transition induced by the partial replacement of Mg²⁺ by Zn²⁺ in the B-site of PMN–PT lattice at x > 0.06. Furthermore, we also investigated the domain structure evolution as functions of temperature and local external electric field in PMN–0.32PT:0.06ZnO ceramics, which exhibited superior piezoelectric property relative to other compositions. We found that the irregular nanodomains are more stable at high-temperature range, and the regular non-180° domains exhibited more complex rotation behavior under local electric field, which probably leads to the thermal stability and piezoelectric property enhancement in the ZnO-modified PMN–0.32PT ceramics.     

Dielectric and piezoelectric properties of Pb(Sc1/2Nb1/2)O3–Pb(Ni1/3Nb2/3)O3–PbTiO3 ternary ceramic materials

The dielectric and electrical properties of xPb(Sc_1/2Nb_1/2)O₃–yPb(Ni_1/3Nb_2/3)O₃–zPbTiO₃ (PSNNT 100x/100y/100z) ternary ceramic materials near the morphotropic phase boundary (MPB) were investigated. The MPB follows on almost linear region between PSNNT 58/00/42 and PSNNT 00/68/32 of the binary systems. The maximum electromechanical coupling factor kp=70·7% was found at PSNNT 36/26/38, where ε₃₃^T/ε₀=3019 and Tc=210°C were obtained. These values are similar to those of the Pb(Sc_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ system and better than those of PZT.     

Relaxation behavior in 0.24Pb(In1/2Nb1/2)O3–0.49Pb(Mg1/3Nb2/3)O3–0.27PbTiO3 ferroelectric single crystal

Dielectric relaxation properties of the ternary relaxor-based ferroelectric 0.24Pb(In_1/2Nb_1/2)O₃–0.49Pb(Mg_1/3Nb_2/3)O₃–0.27PbTiO₃ single crystal have been investigated as a function of temperature (300–570 K) in the frequency range from 100 Hz to 100 kHz. It was found that the variation of the permittivity maximum temperature T_m with frequency obeys the Vogel–Fulcher relationship. The high-temperature (T>T_m) side of the dielectric permittivity deviated from the Curie–Weiss law, but can be described by the Lorenz-type relationship. The coercive field obtained from the polarization hysteresis loops gradually decreases with increasing temperature, and the remnant polarization persists above T_m due to the existence of polar nanoregions (PNRs).     

A new Pb(Lu1/2Nb1/2)O3–PbZrO3–PbTiO3 ternary solid solution with morphotropic region and high Curie temperature

A ceramic ternary system of (1?x?y)Pb(Lu_1/2Nb_1/2)O₃–xPbZrO₃–yPbTiO₃ (PLuN–PZ–PT) has been prepared by two-step synthetic process and characterized by X-ray powder diffraction and electric measurements. A morphotropic phase boundary (MPB) region has been delimited in the ternary system at room temperature. With the PLuN content increasing, the morphotropic phase boundary region becomes broad as well as the dielectric peak. The best comprehensive piezoelectric properties were achieved at MPB composition 0.42PLuN–0.1PZ–0.48PT, with the piezoelectric coefficients d₃₃, the Curie temperature T_c, the planar electromechanical coupling factor K_p, and the remnant polarizations P_r being 367 pC/N, 360 °С, 68% and 35 μС/cm², respectively. The results indicate that the PLuN–PZ–PT ternary ferroelectric material may be a promising candidate for high-power electromechanical transducers that can operate in a large temperature range.     

Effect of Ba(Zn1/3Nb2/3)O3 modification on structure and ferroelectric properties of 0.6Pb(Mg1/3Nb2/3)O3–0.4Pb(Zr0.52Ti0.48)O3 ceramics

In this study, (1−x)[0.6Pb(Mg_1/3Nb_2/3)O₃–0.4Pb(Zr_0.52Ti_0.48)O₃]–xBa(Zn_1/3Nb_2/3)O₃; (1−x)PMNZT60/40–xBZN having x=0, 2.5, 5, 7.5, and 10 mol% ceramics were prepared by mixed oxide powder method and sintered using a two-step process. Phase transitions were investigated by XRD, microstructure by SEM, crystal morphology by TEM, the dielectric and ferroelectric properties by capacitance measurement setup and modified Sawyer-Tower circuit, respectively. The dielectric constant and dielectric loss tangent were measured as functions of both temperature and frequency. The XRD results show the phase transition from tetragonal phase to pseudo-cubic phase with addition of BZN in PMNZT system. Grain size of about 1.23–2.42 μm and crystallite size in a range of 421–2152 nm were obtained. The pure-phase 0.6PMN–0.4PZT ceramics show the normal ferroelectric behavior. The 0.95(PMNZT60/40)–0.05BZN and 0.925(PMNZT60/40)–0.075BZN showed a broad and diffused dielectric properties and the dispersive phase transition, indicating the relaxor ferroelectric behavior. The transition temperature in the BZN-modified PMNZT system is seen to decrease from 166 °C in pure PMNZT60/40 to 102 °C and 54 °C with increasing BZN content to 5 and 10 mol%, respectively. In addition, the maximum dielectric constant is decreased with increasing BZN content. The P–E hysteresis loop measurements show the change from the normal ferroelectric behavior in PMNZT60/40 ceramic to more relaxor behavior that was induced with BZN addition. These results clearly demonstrated the significance of BZN to the electrical responses of the PMNZT60/40 system.     

Microstructure evolution and reaction mechanism of Pb(Zr1/2Ti1/2)O3-Pb(Zn1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3 piezoelectric ceramics with plate-like PbTiO3 template

0.83 Pb(Zr_1/2Ti_1/2)O₃-0.11Pb(Zn_1/3Nb_2/3)O₃-0.06Pb(Ni_1/3Nb_2/3)O₃ (PZNNT) samples with plate-like PbTiO₃ (PT) template were prepared using tape casting technology. The microstructure evolution and reaction mechanism between the matrix and PT template was investigated systematically. The quench heat treatment experiment was designed and the microstructure was evaluated. The results showed that the plate-like PT template has relatively low thermal stability which would decompose to form Pb-rich liquid phase and Ti-rich region at the sintering temperature of 900 °C–1050 °C. Plate-like PT template reacted with the PZNNT matrix materials during the sintering process, which did not contribute to the grain growth orientation for PZNNT matrix. Finally, the mechanism of grain growth for the PZNNT ceramics with plate-like PT template is clarified. This work demonstrated that the thermal stability of plate-like template is one of the key factors for fabricating textured piezoelectric ceramics.     

The evolution of structure and electrical properties for BiFeO3–PbTiO3–Ba(Zr0.3Ti0.7)O3 high-temperature piezoceramics near the morphotropic phase boundary

The development of piezoceramics with high Curie temperature and high piezoelectrical performance has always been a long-cherished goal for many researchers. In this work, we have fabricated 0.55BiFeO₃-(0.45-x)PbTiO₃-xBa(Zr_0.3Ti_0.7)O₃ ternary ceramics near the morphotropic phase boundary (MPB) by conventional solid-state method. XRD patterns indicate that there is an evolution from the tetragonal (T) to pseudo-cubic (PC) phase with BZT content increasing from 0.125 to 0.225. Also, the slim P-E loop transforms into a saturated shape with the decrease of coercive field E_c. Piezoresponse force microscope (PFM) analysis reveals that when x (BZT content) increases, domain density increases. The optimum piezoelectric coefficient d₃₃ (~220 pC/N) is obtained at x = 0.175, while Curie temperature T_C and dielectric loss tanδ are 434 °C and 0.019, respectively. These results show that BF-PT-based piezoceramics are competitive candidates in future high-temperature applications of piezoelectric ceramics.     

Large-strain 0.7Pb(ZrxTi1−x)O3–0.1Pb(Zn1/3Nb2/3)O3–0.2Pb(Ni1/3Nb2/3)O3 piezoelectric ceramics for high-temperature application

0.7Pb(Zr_xTi_1−x)O₃–0.1Pb(Zn_1/3Nb_2/3)O₃–0.2Pb(Ni_1/3Nb_2/3)O₃ (0.7PZT–0.1PZN–0.2PNN, x = 0.44–0.47) piezoelectric powders and ceramics have been prepared through conventional solid-state reaction method. Outstanding piezoelectric and dielectric properties occurred at the morphotropic phase boundary (MPB), which was characterized by the X-ray diffraction spectrum. The MPB composition (x = 0.46) performed high d₃₃ value (641 pC/N), indicating that the system suited large-strain application. The field-induced strain reached 0.25% under a considerably low electric field (0.8 kV/mm) according to the bipolar strain *S–E loops. The effect of the grain size on the aging phenomenon and temperature stability has also been investigated. Due to higher Curie temperature and smaller grain size, the 0.7PZT–0.1PZN–0.2PNN ceramics maintained a high d₃₃ level after depoling treatment, revealing a superior strain capacity for high-temperature application.     

A new multiferroic ternary solid solution system: NdFeO3–Pb(Fe1/2Nb1/2)O3–PbTiO3

Ceramic materials were sintered from powders of the NdFeO₃–Pb(Fe_1/2Nb_1/2)O₃–PbTiO₃ (NF–PFN–PT) ternary system synthesized by the conventional solid reaction method and their multiferroic properties investigated. The structure, electric and magnetic properties of the ternary system have been investigated. The introduction of Pb(Fe_1/2Nb_1/2)O₃ into the NdFeO₃–PbTiO₃ binary system can effectively increase its electric properties. The ternary system exhibits enhanced piezoelectric property with optimal piezoelectric constants d₃₃=143 pC/N, reduced coercive fields E_C=5.78 kV/cm and remnant polarization P_r=12.8 μC/cm² for 0.10NF–0.56PFN–0.34PT, near tetragonal phase region. The Curie temperature (T_C) of the NdFeO₃–Pb(Fe_1/2Nb_1/2)O₃–PbTiO₃ ceramics varies in the range from 108.7 °C to 67.9 °C. The magnetic hysteresis loops show that the ternary system is paramagnetic originating from canting of paramagnetic sublattices in NF–PFN–PT, due to the rare earth ions Nd³⁺ influencing on the exchange interaction between Fe³⁺ ions at the octahedral sites.     

Investigations on electric properties and domain structures of Nd-doped 0.70Pb(Mg1/3Nb2/3)O3–0.30PbTiO3 relaxor ferroelectric ceramics with high piezoelectric properties

Although rare earth neodymium (Nd) doping is common in Pb(Mg1/3Nb2/3)O₃–PbTiO₃ (PMN–PT) single crystals, it is rarely reported in PMN–PT ceramics. To explore the effect of Nd doping on PMN–PT ceramics, PMN–30PT:xNd³⁺ (x = 0%, 1%, 2%, and 3%) relaxor ferroelectric ceramics were fabricated using a solid-state method via two-step sintering. An enhanced piezoelectric charge coefficient (d₃₃) of ∼870 pC/N and a high piezoelectric strain coefficient (d₃₃*) of ∼1025 pm/V were achieved for x = 2%. Through Rayleigh analysis of polarization–electric field (P–E) hysteresis loops under small electric fields, it was found that the dielectric property was mainly influenced by the intrinsic contribution (local lattice distortion). Furthermore, by investigating domain configurations, high piezoelectric properties were found to be associated with the domain size reduction and local structural heterogeneity. The results indicate that the PMN–30PT:xNd³⁺ ceramics is a promising material for electronic devices, and that rare earth Nd doping is an efficient strategy for improving the electronic performance of Pb-based relaxor ferroelectrics.     

Temperature–field phase diagrams in Pb(Zn1/3Nb2/3)O3–4.5%PbTiO3 II

Temperature and field dependences of the dielectric constants under the DC biasing fields along the [011]- and [111]-directions in the cubic coordinate in Pb(Zn_1/3Nb_2/3)O₃–4.5%PbTiO₃ were investigated. The temperature–field phase diagrams were constructed in the field range below 10 kV/cm. It was confirmed that in Pb(Zn_1/3Nb_2/3)O₃–4.5%PbTiO₃ the intermediate tetragonal phase as a ground state of the system exists even without the DC field, and the tetragonal phase disappears in the external field above 4 and 3 kV/cm along the [011]- and [111]-directions, respectively. The field-induced orthorhombic-phase in the field along the [011]-direction was also found.     

Crystal structure and piezoelectric properties of xPb(Mn1/3Nb2/3)O3–(0.2 − x)Pb(Zn1/3Nb2/3)O3–0.8Pb(Zr0.52Ti0.48)O3 ceramics

Pb(Mn_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Zr_0.52Ti_0.48)O₃ (designated as PMnN–PZN–PZT) piezoelectric ceramics were prepared and the effects of PMnN content on the crystal structure and electrical properties were investigated. The results show that the pure perovskite phase forms in these ceramics. The crystal structure changes from tetragonal to rhombohedral and the lattice constant decreases with increase of PMnN content. The morphotropic phase boundary (MPB) of xPMnN–(0.2 ? x)PZN–0.8PZT ceramics occurs where the content of PMnN, x, lies between 0.05 and 0.085 mol. The dielectric constant (?), piezoelectric constant (d₃₃) and Curie temperature (T_c) decrease, while the mechanical quality factor (Q_m) increases with the increase of PMnN content. The ceramic with composition 0.075PMnN–0.125PZN–0.8PZT has the optimal piezoelectric properties, ? is 842, d₃₃ is 215 pC/N, T_c is 320 °C, k_p is 0.57 and Q_m amounts to 1020, which makes it a promising material for high power piezoelectric devices.     

The influence of domain structure on the optical and electrical properties of transparent (Pb,La)(Mg1/3Nb2/3)O3–PbTiO3 ceramics

Transparent (Pb,La)(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PLMNT) ceramics were prepared by two stage sintering method. Two different domain structures were formed in PLMNT transparent ceramics with the same composition by changing the cooling rate. Large strip-like domain structure was formed in rapidly-cooled samples, while fine fingerprint-type domain structure was formed in slowly-cooled samples. The large domain structure in transparent PLMNT ceramics caused light scattering and decreased the transmittance. The cut-off wavelength was also red-shifted for PLMNT ceramics with large domain structure, which was attributed to the inner stress in the ceramics. PLMNT ceramics with different domain structures showed different electrical properties: Compared with PLMNT ceramics with large domain structure, PLMNT ceramics with fine domain structure had smaller coercive field, larger electric field induced strain and lower freezing temperature (T_VF).     

Dielectric,ferroelectric, and energy storage properties of Ba(Zn1/3Nb2/3)O3-modfied BiFeO3–BaTiO3 Pb-Free relaxor ferroelectric ceramics

Pb-free bulk ceramics (1-x)[0.65BiFeO₃-0.35BaTiO₃]-xBa(Zn_1/3Nb_2/3)O₃ were produced by traditional solid-state reaction route. In this experiment, Ba(Zn_1/3Nb_2/3)O₃ (BZN) was introduced to destroy long-range order domains in order to obtain higher energy storage performance. Impedance and XPS analysis indicate that oxygen vacancies exist and participate in relaxation processes at high temperatures. With the increase of BZN content, the dielectric relaxation behavior is improved, the hysteresis loop becomes thinner, remnant polarization decreases, and the breakdown electric field increases to 180 kV/cm in 15BZN. A maximum W_rec (1.62 J/cm³) is eventually reached in 7BZN with great temperature stability. The highest efficiency is 91% in 15BZN with W_rec of 1.28 J/cm³. Charge-discharge tests show that ceramics have a quick discharge time of t_0.9 < 0.1 μs, which makes BZN-doped ceramics a potential candidate for energy storage devices.