High‐Temperature Dielectric Relaxation in Pb(Mg1/3Nb2/3)O3–PbTiO3 Single Crystals

We reported the dielectric properties of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ single crystal in the temperature range of 300–1073 K and the frequency range of 100 Hz–10 MHz. Our results showed the coexistence of both true‐ and pseudo‐relaxor behaviors in the crystal. The true relaxor behavior related to the paraelectric‐ferroelectric phase transition occurs at~423 K. The pseudo‐relaxor behavior appearing at~773 K was found to be related to oxygen vacancies. Further investigation reveals that the pseudo‐relaxor behavior has fine structure: it contains two oxygen‐vacancy‐related relaxation processes. The low‐temperature relaxation process is a dipolar relaxation created by the hopping motions of the oxygen vacancies, and the high‐temperature relaxation process is a Maxwell‐Wagner relaxation caused by the sample/electrode contacts.     

Phase Diagram and Properties of High TC/TR−T Pb(In1/2Nb1/2) O3–Pb(Zn1/3Nb2/3)O3–PbTiO3 Ferroelectric Ceramics

A ternary ferroelectric ceramic system, (1?x?y)Pb(In_1/2Nb_1/2)O₃–xPb(Zn_1/3Nb_2/3)O₃–yPbTiO₃ (PIN–PZN–PT, x = 0.21, 0.27, 0.36, 0.42), was prepared using a two‐step precursor method. The phase structure, dielectric, piezoelectric, and ferroelectric properties of the ternary ceramics were systematically investigated. A morphotropic phase boundary (MPB) was identified by X‐ray diffraction. The optimum piezoelectric and electromechanical properties were achieved for a composition close to MPB (0.5PIN–0.21PZN–0.29PT), where the piezoelectric coefficient d₃₃, planar electromechanical coupling factor k_p, and remnant polarization P_r are 660 pC/N,72%, and 45 μC/cm², respectively. The Curie temperature T_C and rhombohedral to tetragonal phase transition temperature T_R?T were also derived by temperature dependence of dielectric measurements. The strongly “bended” MPB in the PIN–PT system was found to be “flattened” after addition of PZN in the PIN–PT–PZN system. The results demonstrate a possibility of growing ferroelectric single crystals with high electromechanical properties and expanded range of application temperature.     

The Charge Release and Its Mechanism for Pb(In1/2Nb1/2)–Pb(Mg1/3Nb2/3)–PbTiO3 Ferroelectric Crystals Under One‐Dimensional Shock Wave Compression

The charge release and related mechanisms for Pb(In_1/2Nb_1/2)–Pb(Mg_1/3Nb_2/3)–PbTiO₃ (PIN–PMN–PT) ferroelectric crystals under one‐dimensional shock wave compression were investigated using discharge current profile measurement, by which the piezoelectric stress coefficient e₃₁ and the phase transition (from tetragonal to orthorhombic phase) pressure were obtained, being ?2.9 C/m² and 2.3 GPa, respectively. Based on experiment results and thermodynamics analysis, it was found that the one‐dimensional shock compression favored ferroelectric phase, being different from the effect of hydrostatic pressure, which favored paraelectric phase. This phenomenon can be attributed to the crystal anisotropy and electromechanical coupling effects as one‐dimensional shock compression is applied to PIN–PMN–PT ferroelectric crystals.     

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.     

High temperature‐insensitive ferro‐/piezoelectric properties and nanodomain structures of Pb(In1/2Nb1/2)O3–PbZrO3–Pb(Mg1/3Nb2/3)O3–PbTiO3 relaxor single crystals

For rhombohedral (R) Pb(In_1/2Nb_1/2)O₃–PbZrO₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PZ–PMN–PT) relaxor single crystal, high temperature‐insensitive behaviors under different external stimuli were observed (remnant polarization P_r from 30°C to 180°C and piezoelectric strain d₃₃* from 30°C to 116°C). When electric field E ≥ 50 kV/cm in the case of an activation field E_a = 40‐50 kV/cm was applied, it was found that the domain switching was accompanied by a phase transition. The high relaxor nature of the R phase PIN–PZ–PMN–PT was speculated to account for the large E_a and high piezoelectric response. The short‐range correlation lengths extracted from the out‐of‐plane (OP) and in‐plane (IP) nanodomain images, were 64 nm and 89 nm, respectively, which proved the high relaxor nature due to In³⁺ and Zr⁴⁺ ions entering the B‐site in the ABO₃‐lattice and enhancing the disorder of B‐site cations in the R phase PIN–PZ–PMN–PT. The switching process of R nanodomain variants under the step‐increased tip DC voltage was visually revealed. Moreover, the time‐dependent domain evolution confirmed the high relaxor nature of the R phase PIN–PZ–PMN–PT single crystal.     

Preparation and characterization of Pb(Lu1/2Nb1/2)O3–Pb(In1/2Nb1/2)O3–PbTiO3 ternary ferroelectric ceramics with high phase transition temperatures

To explore new relaxor‐PbTiO₃ systems for high‐power and high‐temperature electromechanical applications, a ternary ferroelectric ceramic system of Pb(Lu_1/2Nb_1/2)O₃–Pb(In_1/2Nb_1/2)O₃–PbTiO₃ (PLN–PIN–PT) have been investigated. The phase structure, dielectric, piezoelectric, and ferroelectric properties of the as‐prepared PLN–PIN–PT ceramics near the morphotropic phase boundary (MPB) were characterized. A high rhombohedral‐tetragonal phase transition temperature T_R‐T of 165°C and a high Curie temperature T_C of 345°C, together with a good piezoelectric coefficient d₃₃ of 420 pC/N, were obtained in 0.38PLN–0.20PIN–0.42PT ceramics. Furthermore, for (0.8?x)PLN–0.2PIN–xPT ceramics, the temperature‐dependent piezoelectric coefficients, coercive fields and electric‐field‐induced strains were further studied. At 175°C, their coercive fields were found to be above 9.5 kV/cm, which is higher than that of PMN–PT and soft P5H ceramics at room temperature, indicating PLN–PIN–PT ceramics to be one of the promising candidates in piezoelectric applications under high‐driven fields. The results presented here could benefit the development of relaxor‐PbTiO₃ with enhanced phase transition temperatures and coercive fields.     

Pyrochlore‐Free Ferroelectric 0.64Pb(Ni1/3Nb2/3)O3–0.36PbTiO3 Ceramics Synthesized by the Combustion Method

By adopting Nb₂O₅, HNO₃ and coordination agents EDTA as raw materials, pyrochlore‐free 0.64Pb(Ni_1/3Nb_2/3)O₃–0.36PbTiO₃(0.64PNN–0.36PT) powders were successfully synthesized via a combustion route. Free of pyrochlore phase was realized by the chelation formation of EDTA‐metal ions which isolate niobium and lead oxides and then prevent the formation of pyrochlore phases, therein generate the desired perovskite phases. Comparing the results with similar samples synthesized by the Columbite method, the new 0.64PNN–0.36PT ceramics here shown much better dielectric and ferroelectric performances: a maximum dielectric constant of 22 856 at 1 kHz and a remnant polarization of 21.6 μC/cm² at 40 kV/cm.     

New Antiferroelectric Solid Solution of Pb(Mg1/2W1/2)O3–Pb(Zn1/2W1/2)O3 as Dielectric Ceramics

A new solid solution of (1?x)Pb(Mg_1/2W_1/2)O₃–xPb(Zn_1/2W_1/2)O₃ has been prepared in the form of ceramics by solid‐state reaction with composition x up to 30%. It is found that with the substitution of Zn²⁺ for Mg²⁺ on the B site of the of complex perovskite structure the antiferroelectric (AFE) Curie temperature T_C of PMW increases from 40°C (x = 0) to 67°C (x = 30%), indicating an enhancement of antiferroelectric order, whereas, at the same time, the phase transition becomes more diffuse due to a higher degree of chemical inhomogeneity. X‐ray diffraction analysis indicates that the crystal structure adopts an orthorhombic space group (Pmcn) with a decrease in lattice parameter a, but an increase in b and c as the Zn²⁺ concentration increases. The low dielectric constant (~ 10²), low dielectric loss (tanδ ≈ 10^?3), linear‐field‐induced polarization, and significantly high breakdown field (~ 125 kV/cm) at room temperature make this family of dielectric materials a promising candidate for ceramic insulators.     

Characterization of the High‐Temperature Ferroelectric (100−x−y)BiScO3–(x)Bi(Zr0.5Zn0.5)O3–(y)PbTiO3 Perovskite Ternary Solid Solution

Ternary compositions based on Bi(B′B″)O₃–PbTiO₃‐type compounds have been investigated for high‐temperature piezoelectric applications. Compositions in the ternary were chosen to be near the binary morphotropic phase boundary (MPB) composition of BiScO₃–PbTiO₃ (BS–PT). Ternary compositions in (100?x?y)BiScO₃–(x)Bi(Zr_0.5Zn_0.5)O₃–(y)PbTiO₃ [(100?x?y)BS–xBZZ–yPT] have been investigated with x ≤ 7.5. For compositions with x > 10, the Curie temperature (T_C) decreased below 400°C. Dielectric, piezoelectric, and electromechanical properties were characterized as a function of temperature, frequency, and electric field. Small additions of BZZ were shown to increase the electromechanical properties with only a small loss in T_C. The electromechanical properties were temperature stable up to the depoling temperature. The most promising composition exhibited a T_C of 430°C, piezoelectric coefficient (d₃₃) of 520 pC/N, and a planar coupling factor (k_p) of 0.45 that remained unchanged up to depoling temperature at 385°C.     

Ferroelectric to Relaxor Transition in BaTiO3–Bi(Zn2/3Nb1/3)O3 Ceramics

The (1?x)BaTiO₃–xBi(Zn_2/3Nb_1/3)O₃ (x = 0.01–0.30) ceramics were synthesized by solid‐state reactions. The solubility limit was determined to be x = 0.20. A systematic structural transition from a tetragonal phase (x ≤ 0.034), to a mixture of tetragonal and rhombohedral phases (0.038 ≤ x ≤ 0.20), and finally to a pseudocubic phase (x ≥ 0.22) at room temperature was identified. Dielectric measurement revealed a ferroelectric (x ≤ 0.04) to relaxor (x ≥ 0.06) transition with permittivity peak broadening and flattening, which was further verified by Raman spectroscopy and differential scanning calorimetry (DSC). Activation energies obtained from the Vogel–Fulcher model displayed an increasing trend from ~0.03 eV for x ~ 0.05, to unusually high values (>0.20 eV) for the compositions with x ≥ 0.15. With the increase in Bi(Zn_2/3Nb_1/3)O₃ content, the polarization hysteresis demonstrated a tendency from high nonlinearity to sublinearity coupled with the reduction in remnant polarization and coervice field. The deconvolution of the irreversible/reversible polarization contribution was enabled by first‐order reversal curve distributions, which indicates that the decreasing polarization nonlinearity with the increase in Bi(Zn_2/3Nb_1/3)O₃ concentration could be related with the change from the ferroelectric domain and domain wall contributions to the weakly coupled relaxor behaviors.     

Terahertz Time‐Domain Spectroscopy of 0.73Pb(Mg1/3Nb2/3)O3–0.27PbTiO3 Single Crystal

Lead magnesium niobate titanate is an important ferroelectric material. In this study, the terahertz (THz) transmission properties of a 0.73Pb(Mg_1/3Nb_2/3)O₃–0.27PbTiO₃ single crystal were investigated using a time‐domain spectroscopy method. Complex refractive index and dielectric dispersion functions were determined from the amplitude and phase information derived from time‐domain responses. Based on calculations, it was concluded that the room‐temperature dielectric constant of the single crystal equal to ~30 at 1 THz. This result could be a useful reference for development of ferroelectric‐material‐based THz components and devices.     

Metastable Ferroelectric Phase Induced by Electric Field in xPb(Zn1/3Nb2/3)O3–(1–x)Pb(Zr0.95Ti0.05)O3 Ceramics

A xPb(Zn_1/3Nb_2/3)O₃–(1–x)Pb(Zr_0.95Ti_0.05)O₃ (xPZN–(1–x) PZT) system close to antiferroelectric–ferroelectric (AFE–FE) morphotropic phase boundary has been prepared and investigated. The XRD results reveal PZN addition induces a phase transition from the orthorhombic (AFE) to rhombohedral (FE) phase through a phase coexistence region (AFE+FE). The polarization–electric field (P–E) measurements indicate that the AFE phase can be induced into a metastable FE (FE_m) phase. And the FE_m can recover to AFE around a critical temperature indicated by temperature‐dependent P–E loops. A composition‐temperature phase diagram was generalized within a certain range of PZN content in which an AFE–FE phase boundary connecting orthorhombic antiferroelectric to rhombohedral ferroelectric phase zones is formed near room temperature.     

Perovskite‐Structured BiFeO3–Bi(Zn1/2Ti1/2)O3–PbTiO3 Solid Solution Piezoelectric Ceramics with Curie Temperature About 700°C

In this article, perovskite‐structured BiFeO₃–Bi(Zn_1/2Ti_1/2)O₃–PbTiO₃ (BF–BZT–PT) ternary solid solutions were prepared with traditional solid‐state reaction method and demonstrated to exhibit a coexistent phase boundary (CPB) with Curie temperature of T_C~700°C in the form of ceramics with microstructure grain size of several micron. It was found that those CPB ceramics fabricated with conventional electroceramic processing are mechanically and electrically robust and can be poled to set a high piezoelectricity for the ceramics prepared with multiple calcinations and sintering temperature around 750°C. A high piezoelectric property of T_C = 560°C, d₃₃ = 30 pC/N, ε₃₃^T/ε₀ = 302, and tanδ = 0.02 was obtained here for the CPB 0.53BF–0.15BZT–0.32PT ceramics with average grain size of about 0.3 μm. Primary experimental investigations found that the enhanced piezoelectric response and reduced ferroelectric Curie temperature are closely associated with the small grain size of microstructure feature, which induces lattice structural changes of increased amount ratio of rhombohedral‐to‐tetragonal phase accompanying with decreased tetragonality in the CPB ceramics. Taking advantage of structural phase boundary feature like the Pb(Zr,Ti)O₃ systems, through adjusting composition and microstructure grain size, the CPB BF–BZT–PT ceramics is a potential candidate to exhibit better piezoelectric properties than the commercial K‐15 Aurivillius‐type bismuth titanate ceramics. Our essay is anticipated to excite new designs of high–temperature, high–performance, perovskite‐structured, ferroelectric piezoceramics and extend their application fields of piezoelectric transducers.     

Identification of Substitution Mechanism in Group VIII Metal Oxides Doped Pb(Zn1/3Nb2/3)O3–PbZrO3–PbTiO3 Ceramics with High Energy Density and Mechanical Performance

Group VIII metal oxides, that is, Fe₂O₃, Co₂O₃, and NiO have been introduced to 0.2Pb(Zn_1/3Nb_2/3)O₃–0.8Pb(Zr_0.50Ti_0.50)O₃ (PZN–PZT) to deterministically identify the substitution mechanism and meantime to tailor mechanical and piezoelectric properties in obtaining energy harvesting materials. On the basis of the X‐ray diffraction and Raman analysis, it is clear that the group VIII metal oxides induce a phase transformation from the morphotropic phase boundary to the tetragonal phase side, and the corresponding grain size increases accordingly. It is reasonable to deduce that two types of substitution behaviors coexist in the group VIII metal oxides added PZN–PZT system. Due to the mixed valence of +2 and +3, the foreign doping ions prefer to enter the B site in the perovskite structure, not only substituting for Ti⁴⁺, Zr⁴⁺, and Nb⁵⁺ ions in the inequivalence replacement but also substituting for Zn²⁺ ions in the equivalence replacement. The proposed complex substitution mechanisms can give the full explanation about the grain growth phenomena and the variation in mechanical and electric properties in the modified PZN–PZT system. At the same doping level of 0.3 mol%, the maximum transduction coefficient (d₃₃·g₃₃ = 13120 × 10^?15 m²/N) and good fracture toughness (K_IC = 1.32 MPa m^1/2) are obtained in Co₂O₃ added 0.2PZN–0.8PZT ceramics, which shows great promise as practical materials for energy harvesting device applications.     

Fabrication of Transparent Pb(Mg1/3Nb2/3)O3–PbTiO3 Based Ceramics by Conventional Sintering

Transparent 0.9Pb(Mg_1/3Nb_2/3)O₃–0.1PbTiO₃ (PMN‐PT) based ceramics were prepared by a conventional solid‐state synthesis without using a hot‐press method. The ceramics became transparent when they were sintered in an O₂ atmosphere. The optical transmission increased with decreasing diameter of the calcined powder, which was controlled by the size of zirconia ball‐milling media. Substitution of 3 mol% La for Pb in PMN‐PT further increased the optical transmission to 68% at the wavelength of 2000 nm, which was comparable to that of hot‐pressed Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ based transparent ceramics.     

Structural and Electrical Characteristics of (1−x)Pb(Lu1/2Nb1/2)O3–xPbTiO3 Ceramics with Low PbTiO3

A solid solution of (1?x)Pb(Lu_1/2Nb_1/2)O₃–xPbTiO₃ with composition of 0.01 ≤ x ≤ 0.08 have been prepared successfully. XRD analysis indicates the crystal structure adopts an orthorhombic (O) phase in 0.01 ≤ x ≤ 0.06 interval and becomes the coexistence of O and rhombohedral (R) phase at x = 0.07, then turns into R phase mostly at x = 0.08. In addition, two sets of superlattice reflections due to B‐site ordering and antiparallel cation displacement are distinguished by XRD and the superstructures which arise from antiparallel cation displacement disappear gradually with the increasing x. The grain size increases gradually with the increasing x, and then becomes the bimodal microstructure at x ≥ 0.06 due to the coexistence of O and R phase. The dielectric spectra exhibit Curie temperature decreases from 248°C to 147°C with increasing x from 0.01 to 0.08. As 0.01 ≤ x ≤ 0.04, the samples display typical double hysteresis loops, suggesting antiferroelectric nature, then turn into ferroelectric gradually at x = 0.05. Finally, it exhibit typical ferroelectric hysteresis loops in 0.06 ≤ x ≤ 0.08 interval.     

Fabrication of 0.24Pb(In1/2Nb1/2)O3-0.42Pb(Mg1/3Nb2/3)O3-0.34PbTiO3 transparent ceramics by conventional sintering technique

0.24Pb(In_1/2Nb_1/2)O₃-0.42Pb(Mg_1/3Nb_2/3)O₃-0.34PbTiO₃ transparent ceramics were fabricated by a conventional sintering technique. Through optimization of sintering conditions of calcination and sintering temperatures and time, the obtained ceramics showed high optical transmittance of 53% and 71% at light wavelengths of 1300 and 2000 nm, respectively. The ceramics showed a rhombohedral to tetragonal phase transition at ~120°C and a tetragonal to cubic phase transition at 222°C. These transition temperatures were higher than those of 0.67Pb(Mg_1/3Nb_2/3)-0.33PbTiO₃ ceramics. In addition, the ceramics had a ferroelectric hysteresis loop, a large piezoelectric constant d₃₃ of 407 pC/N, and a planar electromechanical coupling factor k_p of 52%. These results suggest that the transparent ceramics may be used as a temperature-stable, linear electro-optic material.     

Structures and Properties of Pb(Zr0.5Ti0.5)O3−Pb(Zn1/3Nb2/3)O3− Pb(Ni1/3Nb2/3)O3 Ceramics for Energy Harvesting Devices

Piezoelectric ceramics with large energy density coefficient d₃₃·g₃₃ value have been found suitable for piezoelectric energy harvesting applications. In this study, the phase structures and piezoelectric properties of xPb(Zr_0.5Ti_0.5)O₃?yPb(Zn_1/3Nb_2/3)O₃?(1?x?y)Pb(Ni_1/3Nb_2/3)O₃ (xPZT?yPZN?(1?x?y)PNN) ceramic were investigated with systematically varying PZN and PNN components. The ternary phase diagram of PZT?PZN?PNN system was illustrated and the composition region of morphotropic phase boundary (MPB) was determined. Piezoelectric and dielectric measurements verify that the materials in MPB region all present large d₃₃ and d₃₃·g₃₃ values. In particular, very high d₃₃·g₃₃ coefficients of 20162.2 × 10^?15 m²/N and 21026.3 × 10^?15 m²/N are observed from samples 0.75PZT?0.15PZN?0.1PNN and 0.8PZT?0.05PZN?0.15PNN with compositions located on the rhombohedral phase side near MPB because the dielectric coefficient ε₃₃^T/ε₀ decreases faster than the d₃₃ coefficient at this side.     

0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3的析晶行为及助溶剂法生长

研究了0.91Pb(znl/3Nb2/3)O3-0.09PbTiO3(PZNT91/9,摩尔分数)在不同组分和配比熔盐中的析晶行为及其对晶体生长的影响。发现B2O3,PbF2等助溶剂不利于钙钛矿相的析出;而BaTiO3-PbO复合体系虽然能够促进钙钛矿相析出,但晶体析出量很少;只有适当比例的。PbO助溶剂比较适合于生长具有铁电性的钙钛矿相PZNT91/9单晶。助溶剂法生长的工艺参数为:溶质与PbO助溶剂的摩尔比为l:l,泡料温度1 150-1 200℃,泡料时间10 h,晶体生长时降温速度0.8-2℃/h,当温度降到900℃时停止生长,以50℃/h快速冷却至室温。所得晶体为琥珀色,最大尺寸达φ30 mm×15 mm,其压电系数和机电偶合系数分别为2000 pc/N和0.92。     

ZnO-activated formation of phase pure perovskite Pb(In1/2Nb1/2)O3-Pb(Zn1/3Nb2/3)O3-PbTiO3 powder

This paper reports on the phase formation of perovskite Pb(In_1/2Nb_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PZN-PT) powder when doped with 0.04 to 0.83 mol% ZnO. Air calcination of undoped powder mixtures for 4 hours at 800°C resulted in a mixture of Pb₂Zn_0.29Nb_1.71O_6.565 pyrochlore, PIN-PZN-PT perovskite, and In₂O₃. ZnO dopant concentrations as low as 0.04 mol% increased the rate of perovskite formation and resulted in near phase pure perovskite powder of 0.5 μm particle size when heated at 800°C in air. In all cases PbTiO₃ and Pb(In_1/2Nb_1/2)O₃ formed prior to PIN-PZN-PT formation. ZnO doping promotes perovskite phase formation by increasing the reactivity of the intermediate pyrochlore phase by substituting Zn²⁺ on Nb⁵⁺ sites and forming oxygen vacancies when heated in air. Heating in high resulted in an incomplete reaction and a mixture of perovskite and pyrochlore whereas low resulted in phase separation into a mixture of rhombohedral perovskite, tetragonal perovskite, and pyrochlore. The sensitivity clearly shows that oxygen vacancies due to ZnO-doping are critical for synthesis of phase pure PIN-PZN-PT powder.