Electromechanical Properties of Pb(Yb1/2Nb1/2)O3-PbZrO3-PbTiO3 Ceramics

The electromechanical and electric-field-induced strain properties of x Pb(Yb_1/2Nb_1/2)O₃· y PbZrO₃·(1− x − y )PbTiO₃ ( x = 0.12, 0.25, 0.37; y = 0.10–0.40) ceramics have been studied systematically as a function of Pb(Yb_1/2Nb_1/2)O₃ (PYN) content and PbZrO₃/PbTiO₃ (PZ/PT) ratio. In addition, the effect of MnO₂ on the electromechanical properties of 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ was also investigated. The maximum transverse strain values of 1.6 × 10⁻³ for x = 0.12, 1.45 × 10⁻³ for x = 0.25, and 1.36 × 10⁻³ for x = 0.37 were obtained at the compositions which were regarded as the morphotropic phase boundary (MPB). The transverse strain was maximized at the MPB composition. The value of the maximum electromechanical coupling coefficient was 0.69 for y = 0.40 and x = 0.12 composition. In the 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ composition, the temperature of the maximum dielectric constant decreased and the grain size increased with an addition of MnO₂. The electromechanical coupling coefficient decreased while the mechanical quality factor rapidly increased with an addition of MnO₂. These resulted mainly from the acceptor effect of manganese ions that were produced by doping MnO₂ into the perovskite structure.     

Dielectric Properties of Pb(Fe2/3W1/3)O3–PbTiO3 Solid-Solution Ceramics

The dielectric properties of (1− x )Pb(Fe_2/3W_1/3)O₃· x PbTiO₃ solid solutions were investigated from 10² to 10⁶ Hz in the temperature range 150–600 K. The phase transition of Pb(Fe_2/3W_1/3)O₃ (PFW) was shifted by PbTiO₃ (PT) additions to higher temperatures at a rate of 6.3 K/mol% of PT. The temperature dependence of dielectric permittivity showed a sharper transition as the PT content increased. Dielectric measurements in a wide temperature range showed the presence of a second set of dielectric peaks at higher temperatures (350–600 K), besides the ferroelectric–paraelectric phase transition. This second set of peaks vanished when the samples were annealed in nitrogen. The activation energy values for the second relaxation varied between 0.50 and 0.63 eV, in agreement with the conduction activation energy determined for each sample. This relaxation is apparently related to electron holes.     

Effects of Calcium Substitution on the Structural and Microwave Dielectric Characteristics of [(Pb1−xCax)1/2La1/2](Mg1/2Nb1/2)O3 Ceramics

The effects of calcium substitution on the structural and microwave dielectric characteristics of [(Pb_{1− x} Ca _x )_1/2La_1/2](Mg_1/2Nb_1/2)O₃ ceramics (with x = 0.01–0.5) were investigated. All the materials were observed to have an ordered A(B_1/2^'B_1/2^")O₃-type perovskite structure; however, the space group of the structure changed from Fm 3 m to Pa 3 as the calcium content increased to x = 0.1, and then from Pa 3 to R 3¯ at the x = 0.5 composition. During the structural evolution, the lattice parameter of the perovskite cell decreased linearly, and the dielectric constant ( k ) also decreased, from k = 80 to k = 38. However, the product of the quality factor and the resonant frequency ( Q × f ) increased from 50 000 GHz to 90 000 GHz as the calcium content increased. Also, the temperature coefficient of resonant frequency (τ_ƒ) gradually changed from 120 ppm/°C to −40 ppm/°C as the calcium content increased. At the x = 0.3 composition, a combination of properties— k ∼ 50, Q × f ∼ 86 000 GHz, and τ_ƒ∼ 0 ppm/°C—can be obtained.     

Dielectric and Piezoelectric Properties of the Morphotropic Phase Boundary Composition in the (0.8−x) Pb(Mg1/3Ta2/3)O3−0.2PbZrO3−xPbTiO3 Ternary System

Morphotropic phase boundary (MPB) compositions separating rhombohedral and tetragonal phases in the (1− x − y )Pb(Mg_1/3Ta_2/3)O₃– y PbZrO₃– x PbTiO₃ (PMT–PZ–PT100 x ) ternary solid solution system were characterized using X-ray diffraction and dielectric, piezoelectric properties. This work focused on compositions with a PZ content fixed at y =0.2, with an MPB composition found to be located at x =0.4. Piezoelectric coefficients and dielectric permittivity were found to be on the order of d ₃₃=580 pC/N and 4100, respectively. Acceptor modification using manganese was found to induce a "hardening" effect in 0.4PMT–0.2PZ–0.4PT, with decreased piezoelectric coefficients d ₃₃ and dielectric loss and increased mechanical quality factor Q . Piezoelectric coefficients d ₃₃, Q values, and dielectric loss were found to be 500 pC/N, 2000, and 0.4%, respectively, for 0.4PMT–0.2PZ–0.4PT with MnO₂ dopant levels around 0.5 wt%. The figure of merit (product of Q and d ₃₃) was found to be on the order of 1 × 10⁶, significantly higher when compared with other hard piezoelectric PZT materials. Specifically, the PMT–PZ–PT materials may be attractive candidates for high-power ultrasonic applications, particularly fine-scale components that require relating high permittivities.     

Synthesis of 0.4Pb(Mg1/3Nb2/3)O3–0.3Pb(Mg1/2W1/2)O3–0.3PbTiO3 Ceramics by Metal Alkoxide Method, and Its Dielectric Properties

0.4Pb(Mg_1/3Nb_2/3)O₃–0.3Pb(Mg_1/2W_1/2)O₃–0.3PbTiO₃+ x MgO ( x = 0 to 0.04) were prepared by a metal alkoxide method. The percent of perovskite phase of the calcined powders increased with increased calcination temperatures. About 89% of perovskite phase was obtained at 1050°C. The dielectric constant of the pellets fired at 1100°C was increased by the addition of 10 wt% excess Mg(OC₂H₅)₂ and had a maximum value of 7532 at 1 kHz.     

Unique Dielectric Behavior of 0.6Pb(Ni1/2W1/2)O3·0.4PbTiO3 Derived from Mechanical Activation

0.6Pb(Ni_1/2W_1/2)O₃·0.4PbTiO₃(0.6PNW·0.4PT) of complex perovskite structure is successfully synthesized by mechanical activation of mixed oxide composition, followed by sintering at 950°C. It exhibits a considerably stable temperature dependence of dielectric constant over the wide temperature range of −120° to 20°C, although there occurs a dielectric peak at around 74°C. Raman spectroscopic studies show the coexistence of tetragonal and pseudocubic perovskite phases on sintering at 950°C, which are attributed to the inhomogeneous distribution of PbTiO₃ arising from mechanical activation. The dielectric behavior can be fine tuned by thermal annealing at 750°C, leading to phase redistribution in PNW-PT.     

Phase Structure and Electrical Properties of (K0.48Na0.52)(Nb0.95Ta0.05)O3-LiSbO3 Lead-Free Piezoelectric Ceramics

(1− x )(K_0.48Na_0.52)(Nb_0.95Ta_0.05)O₃– x LiSbO₃ [(1− x )KNNT− x LS] lead-free piezoelectric ceramics were prepared by the conventional solid-state sintering method. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal phases was identified in the composition range of 0.03< x <0.05. The ceramics near the MPB exhibit a strong compositional dependence and enhanced electrical properties. The (1− x )KNNT– x LS ( x =0.04) ceramics exhibit good electrical properties ( d ₃₃=250 pC/N, k _p=45.1%, k _t =46.3%, T _c=348°C, T _{o − t} =74°C, P _r=25.9 μC/cm², E _c=10.7 kV/cm, ɛ_r∼1352, tan δ∼3%). These results show that (1− x )KNNT– x LS ceramic is a promising lead-free piezoelectric material.     

Aging Behavior of xPb(Fe2/3W1/3)O3· (1 –x)Pb(Fe1/2Nb1/2)O3 Ceramic

The aging behavior of a series of lead perovskite dielectrics with the compositions x Pb(Fe_2/3W_1/3)O₃·(1 – x )Pb(Fe_1/2-Nb_1/2)O₃, where 0 ≤ x ≤ 1, and the effect of dopants were studied. Below the Curie temperature ( T _c), the capacitance and the dissipation factor (tan δ) decrease approximately linearly with logarithmic time. The aging rate depends on the temperature difference, Δ T , between the aging temperature and T _c, and on the dopant concentration, but is independent of the measurement frequency between 1 and 1000 kHz. The maximum aging rate is about 3% per decade of time for capacitance and 5% per decade for tan δ at 1 mol% dopant concentration, and increases to 6.3% for capacitance and 8.5% for tan δ at 0.7 mol% dopant concentration. These results are consistent with an aging mechanism caused by changing ferroelectric domain structure with time, as proposed for BaTiO₃.     

Ferroelectric and Structural Properties of the Pb(Sc1/2Nb1/2)1-x,Tix,O3 System

Extensive solid solution was observed in the system Pb(Sc_1/2/,Nb_1/2,)_1-x,Ti_x,O₃. In the range 0 ≤ x ≤ 0.425 a rhombohedral ferroelectric phase was stable at 25° C. In the range 0.45 ≤ x ≤ 1.00 a tetragonal ferroelectric phase was stable at this temperature. The phase diagram of the system below 500° C strongly resembles that of PbZrO₃−PbTiO₃. The compound Pb(Sc_1/2Nb_1/2)O₃ exhibited rhombohedral perovskite cell symmetry below the ferroelectric ↔ paraelectric transition temperature, and the angle a was acute. The radial coupling coefficient was 0.46 for the composition Sc_1/2Nb_1/2)_0.575Ti_0.4250O₃. At 25°C this composition consisted primarily of the rhombohedral phase with a small amount of the tetragonal phase present. The ferroelectric ↔ paraelectric transition occurred over a temperature range in the rhombohedral phase field. The spontaneous polarization was finite at temperatures considerably above the temperature of the permittivity maximum for a given rhombohedral solid solution.     

Mechanical Activation-Assisted Synthesis of Pb(Fe2/3W1/3)O3

Perovskite Pb(Fe_2/3W_1/3)O₃ (PFW) was prepared via a mechanical activation-assisted synthesis route from mixed oxides of PbO, Fe₂O₃, and WO₃. The mechanically activated oxide mixture, which exhibited a specific area of >10 m²/g, underwent phase conversion from nanocrystalline lead tungstate (PbWO₄) and pyrochlore (Pb₂FeWO_6.5) phases on sintering to yield perovskite PFW, although the formation of perovskite phase was not triggered by mechanical activation. When heated to 700°C, >98% perovskite phase was formed in the mechanically activated oxide mixture. The perovskite phase was sintered to a density of ∼99% of theoretical density at 870°C for 2 h. The sintered PFW exhibited a dielectric constant of 9800 at 10 kHz, which was ∼30% higher than that of the PFW derived from the oxide mixture that was not subjected to mechanical activation.     

Low-Loss Microwave Dielectrics Using Mg2(Ti1−xSnx)O4 (x=0.01–0.09) Solid Solution

Low-loss ceramics having the chemical formula Mg₂(Ti_{1− x} Sn _x )O₄ for x ranging from 0.01 to 0.09 have been prepared by the conventional mixed oxide route and their microwave dielectric properties have been investigated. X-ray powder diffraction patterns indicate the corundum-structured solid solutions for the prepared compounds. In addition, lattice parameters, which linearly increase from 8.4414 to 8.4441 Å with the rise of x from 0.01 to 0.09, also confirm the forming of solid solutions. By increasing x from 0.01 to 0.05, the Q × f of the specimen can be tremendously boosted from 173 000 GHz to a maximum 318 000 GHz. A fine combination of microwave dielectric properties (ɛ_r∼15.57, Q × f ∼318 000 GHz at 10.8 GHz, τ_f∼−45.1 ppm/°C) was achieved for Mg₂(Ti_0.95Sn_0.05)O₄ ceramics sintered at 1390°C for 4 h. Ilmenite-structured Mg(Ti_0.95Sn_0.05)O₃ (ɛ_r∼16.67, Q × f ∼275 000 GHz at 10.3 GHz, τ_f∼−53.2 ppm/°C) was detected as a second phase. The presence of the second phase, however, would cause no significant variation in the dielectric properties of the specimen, because the second phase properties are very similar to the primary phase. These unique properties, in particular, low ɛ_r and high Q × f , can be utilized as a very promising dielectric material for ultra-high-frequency applications.     

Influence of Non-Stoichiometry on the Structure and Properties of Ba(Zn1/3Nb2/3)O3 Microwave Dielectrics: I. Substitution of Ba3W2O9

A narrow region of Zn-vacancy-containing cubic perovskites was formed in the (1− x )Ba₃(ZnNb₂)O₉−( x )Ba₃W₂O₉ system up to 2 mol% substitution ( x =0.02). The introduction of cation vacancies enhanced the stability of the 1:2 B-site ordered form of the structure, Ba(Zn_{1− x} □ _x )_1/3(Nb_{1− x} W _x )_2/3O₃, which underwent an order–disorder transition at 1410°C, ∼35° higher than pure Ba(Zn_1/3Nb_2/3)O₃. The Zn vacancies also accelerated the kinetics of the ordering reaction, and samples with x =0.006 comprised large ordered domains with a high lattice distortion ( c/a =1.226) after a 12 h anneal at 1300°C. The tungstate-containing solid solutions can be sintered to a high density at 1390°C, and the resultant ordered ceramics exhibit some of the highest microwave dielectric Q factors ( Q × f =1 18 000 at 8 GHz) reported for a niobate-based perovskite.     

Effect of Simultaneous Addition of BiFeO3 and Ba(Cu0.5W0.5)O3 on Lowering of Sintering Temperature of Pb(Zr,Ti)O3 Ceramics

Sintering of 0.5-wt%-MnO₂-added Pb(Zr_0.53Ti_0.47)O₃ ceramics progresses at 935°C for 50 min by the addition of complex oxides of perovskite-type crystal structure, BiFeO₃ and Ba(Cu_0.5W_0.5)O₃. In order to elucidate the low-temperature sintering mechanism of Pb(Zr,Ti)O₃ ceramics, the shrinkage and the evolution of the microstructure of a compacted body during heating were studied. It has been shown that the densification process was separated into the following three stages: the rearrangement of grains, the grain boundary diffusion of atoms, and then grain growth. Also, microstructural and elemental analyses of the ceramics revealed the existence of an amorphous phase at the grain boundaries predominantly composed of lead and copper oxides. Consequently, this process can be facilitated by the occurrence of a transient liquid phase corresponding to the above amorphous phase.     

High Piezoelectric and Dielectric Properties of La-Doped 0.3Pb(Zn1/3Nb2/3)O3–0.7Pb(ZrxTi1−x)O3 Ceramics Near Morphotropic Phase Boundary

La-doped 0.3Pb(Zn_1/3Nb_2/3)O₃–0.7Pb(Zr _x Ti_{1− x} )O₃ ( x =0.5–0.53) piezoelectric ceramics with pure perovskite phase were synthesized by a two-step hot-pressing route. The piezoelectric properties of various compositions near the morphotropic phase boundary (MPB) were systematically investigated. Not only was the exact MPB of this system determined via X-ray diffractometry analysis, but also the peak of piezoelectric properties was found near the MPB. The optimum piezoelectric properties of this series were observed in the specimen with Zr/Ti=51/49. The piezoelectric coefficient ( d ₃₃) and electromechanical coupling factor ( k _p) were 845 pC/N and 0.70, respectively, which have not been reported in this system so far. Large permittivity (ɛ_r=4088) and permittivity maximum (ɛ_m=29 500) were also obtained for the poled specimens. The temperatures ( T _max) of the permittivity maxima ranged from 206° to 213°C with various Zr/Ti ratios.     

Kinetics of Templated Grain Growth of 0.65Pb(Mg1/3Nb2/3)O3·0.35PbTiO3

Single-crystal layers of 0.65Pb(Mg_1/3Nb_2/3)O₃·0.35PbTiO₃ (PMN-35PT) were grown heteroepitaxially on {001}-BaTiO₃ template crystals. A {001}-BaTiO₃ crystal was embedded in a fine-grained matrix of PMN-35PT containing excess PbO and heated between 950° and 1150°C for 0–5 h. The initial growth of the PMN-35PT on the {001} surface and the growth of the matrix grains both displayed a t ^1/3 dependence which is characteristic of diffusion-controlled growth. Growth was limited to ∼100–150 μm due to the significantly reduced driving force at longer times because of matrix coarsening and porosity evolution.     

Structure and Microwave Dielectric Properties of Hexagonal Ba[Ti1−x(Ni1/2W1/2)x]O3 Ceramics

Microwave dielectric ceramics with the composition of Ba[Ti_{1− x} (Ni_1/2W_1/2) _x ]O₃ ( x =0.4–0.6) were prepared by a solid-state reaction method. The evolution of the crystalline phases was investigated by X-ray powder diffraction analysis. A cubic-to-hexagonal phase transition occurred between 1000° and 1300°C. The phase transition is irreversible; thus, the hexagonal phase remains stable at room temperature. The X-ray powder diffraction data for x =0.5 were refined using the Rietveld method. It was identified as a h -BaTiO₃-type hexagonal perovksite with the space group of P 6₃/ mmc . It also reveals that random occupancy of Ti⁴⁺ and W⁶⁺ ions occurs in the B-site substructures, whereas Ni²⁺ ions exclusively occupy the octahedral site in the corner-sharing octahedron. The dielectric properties of dense-sintered ceramics were characterized at microwave frequencies. With an increase in x from 0.4 to 0.6, the Q × f value increased from 26 700 to 42 000 GHz, whereas ɛ_r decreased from 29.8 to 20.0, and τ_f from +6.5 to −9.9 ppm/°C.     

Low Temperature Coefficient of Resonance Frequency Composition in the System Pb(Zr,Ti)O3—Pb(Mn1/3 Nb2/3)O3

Pb(Zr,Ti)O₃–Pb(Mn_1/3 Nb_2/3)O₃ (PZT–PMnN) system has been studied for high-power piezoelectric applications. This study investigates this system to find out the composition with high-power density piezoelectric characteristics and low tem-perature coefficient of resonance frequency (TCF). It was found that the composition 0.9PZT–0.1PMnN (Zr/Ti = 0.51/0.49) modified with 6 mol% Sr exhibits a TCF of −8 ppm/°C (−20 to +80°C). Further, the dielectric and piezoelectric properties of this composition are as follows: k _p= 0.53; Q _m= 800; d ₃₃= 274; ε₃₃/ε₀= 1290 and tan δ=1.1%, which shows the suitability of this composition for ultrasonic devices used under fluctuating thermal environment.