Ac behaviour and phase transition in PLZT 6/80/20 ferroelectric ceramics

The Ac behaviour of PLZT 6/80/20 ferroelectric ceramics was analyzed around and above the phase transition. Two relaxation processes are identified, showing that the so-called ‘universal relaxation law’ holds for the ceramics. A critical point in the values of the Ac conductivity, around the temperature corresponding to the maximum of the dielectric losses, is observed below the transition temperature due to the relaxor behaviour. The frequency dependence of the Ac conductivity at various temperatures and the hysteresis loops show classical relaxor behaviour with a diffuse phase transition.     

Bias field effects on the dielectric properties of 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3 single crystals with different orientations

The domain states and phase transitions in 0.67Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ single crystals were investigated by studying their relative permittivity under various dc bias at constant heating and cooling rates. The orientation dependence of the bias field effect was revealed by examining the temperature dependence of relative permittivity as a function of crystal orientation (the 〈111〉, 〈011〉 and 〈001〉 directions) and dc bias field. The crystals basically have a macrodomain rhombohedral ferroelectric state in the ferroelectric phase under zero dc bias. External bias field could modulate the domain state and induce a stable macrodomain state in the crystals. Also, it is proposed that the dc bias applied along the 〈001〉 or 〈011〉 direction could induce a tetragonal ferroelectric phase or an orthorhombic ferroelectric phase, respectively, in an intermediate temperature range.     

Effects of composition on phase structure and electrical properties of (K0.5Na0.5)0.90Li0.06Sr0.02Nb(1−x)SbxO3 ceramics

Lead-free (K_0.5Na_0.5)_0.90Li_0.06Sr_0.02Nb_(1−x)Sb_xO₃ (KNLSN-Sb_x) ceramics were synthesized by ordinary sintering technique. The compositional dependence of phase structure and electrical properties of the ceramics was systematically investigated. All samples possessed pure perovskite structure, showing room temperature symmetries of orthorhombic at x<0.01, coexistence of orthorhombic and tetragonal phases at x=0.01, and tetragonal at 0.02≤x≤0.05. The temperature of the polymorphic phase transition (PPT) was shifted to lower temperature and dielectric relaxor behavior was induced by increasing Sb content. The samples near the coexistence region (x=0.01) exhibited enhanced electrical properties: d₃₃∼145 pC/N, k_p∼38% and P_r∼20.4 μC/cm².     

TiO2-nonstoichiometry dependence on piezoelectric properties and depolarization temperature of (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06Ti_xO_1+2x lead-free piezoceramics with x varying from 0.97 to 1.03 were fabricated and characterized in order to investigate the effects of TiO₂-nonstoichiometry on the piezoelectric properties and depolarization temperature of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition. X-ray diffraction (XRD) analysis showed that all samples have a single phase of perovskite structure with rhombohedral symmetry. Piezoelectric and dielectric measurements revealed that deficiency of TiO₂ leads to an increase in the piezoelectric coefficient (d₃₃), free relative permittivity (), and loss tangent (tan δ) besides an increase in the electromechanical coupling coefficient (k_p) within a certain amount, while excess of TiO₂ results in a decrease in k_p, d₃₃, and , but an increase in tan δ. Depolarization temperature (T_d) measurement indicated a decrease and an increase in T_d as a result of increasing TiO₂ deficiency and TiO₂ excess, respectively. This TiO₂-nonstoichiometry also induced changes in the remanent polarization (P_r) and coercive field (E_c) of the ceramics.     

Observation of giant dielectric constant in CdCu3Ti4O12 ceramics

Although CdCu₃Ti₄O₁₂ is isostructural to CaCu₃Ti₄O₁₂, the room temperature low-frequency dielectric constant of the former compound was reported to be ∼400, only 1/25 of that of the latter material [M.A. Subramanian, et al., J. Solid State Chem. 151 (2000) 323]. In this communication, we report that the dielectric constant of CdCu₃Ti₄O₁₂ can be remarkably increased by elevating the sintering temperature. The room temperature dielectric constant at 100 kHz achieves 9000, almost as much as that of CaCu₃Ti₄O₁₂, for the sample sintered at 1283 K. The appearance of giant dielectric constant in CdCu₃Ti₄O₁₂ is explained in terms of internal barrier layer capacitance (IBLC) effect with the subgrain boundary as the barrier. Our result supplies an approach in searching for new giant-dielectric-constant materials in the CaCu₃Ti₄O₁₂ family.     

Ti deficiency effect on the dielectric response of CaCu3Ti4O12 ceramics

Single phase ceramics CaCu₃Ti_4.0O₁₂ and CaCu₃Ti_3.9O₁₂ have been prepared using the traditional solid-state reaction method. Compared with the stoichiometric ceramics CaCu₃Ti_4.0O₁₂, Ti-deficient ceramics CaCu₃Ti_3.9O₁₂ have the larger lattice parameter, the higher force constant, and smaller dielectric constant and the lower dissipation factor, although their fundamental characters of dielectric response are similar. Their characteristic relaxation frequencies are not well fitted with the Arrhenius Law but a tentatively supposed relation. With the Cole-Cole Law, the fitted broadened factors of dissipation peaks are 0.5433 and 0.8651 for CaCu₃Ti_3.9O₁₂ and CaCu₃Ti_4.0O₁₂, respectively. All facts mentioned above imply that mutually correlated motion of Ti ions or defects may be expected to be responsible for the giant dielectric constant and high dissipation factor of CaCu₃Ti_4.0O₁₂.     

Sub-coercive field dynamic hysteresis in morphotropic phase boundary composition of Pb(Zr1/2Ti1/2)O3-Pb(Zn1/3Nb2/3)O3 ceramic and its scaling behavior

Sub-coercive field dynamic ferroelectric hysteresis of a morphotropic phase boundary composition of the PZT-PZN ceramic was investigated under influence of the compressive stress. The scaling relation of hysteresis area 〈A〉 against frequency f, field amplitude E₀, and stress σ took a form of , which is not different significantly to that of other PZT-PZN compositions with pure tetragonal or rhombohedral structure, as well as to that of soft and hard PZT bulk ceramics. This study suggested that the domain structures, not ceramic compositions, played a key role in controlling dynamic hysteresis behavior of ferroelectric materials.     

Electric-field dependence of dielectric properties of sol-gel derived Ba(Zr0.2Ti0.8)O3 ceramics

The effect of a dc bias field on the diffuse phase transition and nonlinear dielectric properties of sol-gel derived Ba(Zr_0.2Ti_0.8)O₃ (BZT) ceramics are investigated. Diffuse phase transitions were observed in BZT ceramics and the Curie–Weiss exponent (CWE) was γ∼2.0. The dielectric constant versus temperature characteristics and the γ in the modified Curie–Weiss law, ε ⁻¹=ε _m ⁻¹[1+(T−T _m ) ^γ /C₁](1≤γ≤2), as a function of the dc bias field was obtained for BZT ceramics. The results indicated that γ is a function of dc bias field, and the γ value decreased from 2.04 to 1.73 with dc bias field increasing from 0 to 20 kV/cm. The dielectric constant decreases with increasing dc bias field, indicating a field-induced phase transition. The dc bias field has a strong effect on the position of the dielectric peak and affects the magnitude of the dielectric properties over a rather wide temperature range. The peak temperature of the dielectric loss does not coincide with the dielectric peak and an obvious minimum value for the dielectric loss at the temperature of the dielectric peaks is observed. At room temperature, 300 K, the high tunability (K=80%), the low loss tangent (≈0.01) and the large FOM (74), clearly imply that these ceramics are promising materials for tunable capacitor-device applications.     

Dielectric properties and phase transitions of (Pb0.87La0.02Ba0.1)(Zr0.6Sn0.4−xTix)O3 ceramics with compositions near AFE/RFE phase boundary

The electrical properties and phase transition behavior of (Pb_0.87La_0.02Ba_0.1)(Zr_0.6Sn_0.4−xTi_x)O₃ solid solutions (PLBZST, 0.04≤x0.2) were investigated by the X-ray diffraction, permittivity, pyroelectric current, and P-E electric hysterisis loops. As the composition x increased from 0.04 to 0.2, the antiferroelectric ceramics (x≤0.07, AFE) with tetragonal phase changed to the ferroelectric relaxors (RFE, 0.09≤x). AFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to −100 °C) due to a frustration between AFE and FE state. With an increase in composition x, electrically field-induced AFE-FE switching field (E_AFE-FE) and AFE-paraelectric (PE) phase transition temperature (T_c) are depressed in the temperature (T)-Ti composition (x) phase diagram, a FE-AFE-PE triple phase point (T_tr) with the lowest transition temperature occurred at x=0.09. The pyroelectric currents under an application of various external electric field (E) were measured to identify a T-E phase diagram of the PLBZST compound.     

Dielectric and piezoelectric properties of lead-free (Na0.5K0.5)NbO3-SrTiO3 ceramics

In this article, we report successful preparation of dense [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ (x=0.005-0.100) ceramics by ordinary sintering in air. The dependence of phase structure on doping content of SrO and TiO₂ has been determined by the X-ray diffraction technique. It was found that the crystal structure changed from orthorhombic to tetragonal at x≈0.040. Dielectric study revealed that the dielectric relaxor behavior was induced by doping of SrO and TiO₂ into (Na_0.5K_0.5)NbO₃. The samples in the composition range from x=0.005 to 0.020 exhibited excellent electrical properties, piezoelectric constant of electromechanical planar and thickness coupling coefficients of k_p=26.6-32.5% and k_t=39.8-43.8%. The results show that the [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics are one of the promising lead-free materials for electromechanical transducer applications.     

Dependence of high electric-field-induced strain on the composition and orientation of Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals

Electric-field-induced strain behavior of (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMNT) crystals with different orientations and compositions was investigated for use as electromechanical actuators. Crystallographically, high strains with low hysteresis were achieved for 〈001〉 oriented rhombohedral crystals (29%≤x≤31%) near a morphotropic phase boundary, rather than 〈110〉 and 〈111〉. Domain instability could explain inferior strain levels and large hysteresis for 〈110〉 and 〈111〉 oriented crystals. Ultrahigh strain levels up to 1.8% could be achieved for 〈001〉 oriented PMNT crystals, being related to an E-field induced phase transition. −2 kV/cm negative E-field can be applied to PMNT ferroelectric material with low hysteresis. High strain with low hysteresis makes PMNT crystals promising candidates for high performance solid-state actuators.     

Characterization of lead free (K0.5Na0.5)NbO3-LiSbO3 piezoceramic

(K_0.5Na_0.5)NbO₃ (KNN) based lead free ceramics have been fabricated by a solid state reaction. In this work, LiSbO₃ (LS) modified KNN based ceramics were sintered at atmospheric pressure and high density (>96% theoretical) was obtained. The detailed elastic, dielectric, piezoelectric and electromechanical properties were characterized by using the resonance technique combined with the ultrasonic method. The full set of material constants for the obtained polycrystalline ceramics were determined and compared to the pure hot pressed KNN counterpart. KNN-LS polycrystalline ceramic was found to have higher elastic compliance, dielectric permittivity and piezoelectric strain coefficients, but lower mechanical quality factor, when compared to pure KNN, exhibiting a “softening” behavior. However, a high coercive field (∼17 kV/cm) was found for the LS modified KNN material. The properties as a function of temperature were determined in the range of −50-250 ^°C, showing a polymorphic phase transition near room temperature, giving rise to improved piezoelectric behavior.     

Investigations of structural, dielectric and ferroelectric behavior of europium substituted SrBi2Ta2O9 ferroelectric ceramics

Europium substituted samples of the compositions Sr_1−xEu_xBi₂Ta₂O₉ (x=0.0,0.025,0.050,0.10 and 0.20) were synthesized by solid state reaction method and studied for their structural, dielectric and ferroelectric properties. The X-ray diffractograms confirmed the formation of single phase layered perovskite structure in all the samples. The temperature variation of dielectric constant shows that the Curie temperature (T_c) decreases on increasing concentration of europium. The dielectric loss reduces significantly with europium addition. The P-E studies of the Eu-substituted SBT ceramics show that the remanent polarization increases with increasing concentration of europium.     

Phase transformation in (0.90−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3-0.10PbZrO3 piezoelectric ceramic: X-ray diffraction and Raman investigation

Piezoelectric ceramics with compositions of (0.90−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃-0.10PbZrO₃, x=0.28, 0.31, 0.34, 0.37, 0.40 and 0.43, were prepared using the conventional columbite precursor method, and their structural phase transformation and piezoelectric behaviors near the morphotropic phase boundary (MPB) have been systematically investigated as a function of PbTiO₃ content. X-ray diffraction (XRD) results demonstrate that the structure of the ceramics experiences a gradual transition process from rhombohedral phase to tetragonal phase with the increasing of PbTiO₃ content, and that compositions with x=0.34-0.40 lie in the MPB region of this ternary system. A Raman spectra investigation of the ceramic samples testified to the transformation process of rhombohedral phase to tetragonal phase by comparing the relative intensities of tetragonal E(2TO₁) mode and rhombohedral phase R_h mode. The structure information was also correlated to the parabola change of the piezoelectric constant; the maximum piezoelectric constants were obtained near the MPB region.     

Relaxor behaviour in PZN-PT-BT ferroelectric ceramics

The relaxor behaviour of the (Pb_0.8Ba_0.2)[(Zn_1/3Nb_2/3)_0.7Ti_0.3]O₃ ferroelectric ceramic is presented. A strong dispersion of the maximum of the dielectric permittivity (ε′) below the transition temperature (T_m) is observed, which shift towards higher temperatures with increasing frequency. There is a strong deviation from the Curie-Weiss law. The results are fitted by using the Volger-Fulcher relationship, showing typical behaviour of a spin glass system. The hysteresis loops suggest relaxor behaviour.     

Ferroelectric properties of Pr and Nb co-substituted Sr0.8Bi2.2Ta2O9 thin films

Thin film of both A- and B-site co-substituted Sr_0.8Bi_2.2Ta₂O₉ (SBT) by Pr³⁺ and Nb⁵⁺, i.e. Sr_0.8Pr_0.1Bi_2.1Ta_1.5Nb_0.5O₉ (SPBTN) was fabricated on Pt/Ti/SiO₂/Si substrates by metalorganic decomposition method. The Nb⁵⁺ substitution at B-site and Pr³⁺ substitution at A-site enhanced the remanent polarization and reduced the coercive field of the films, respectively. The remanent polarization (2P_r) value of the SPBTN film was 22 μC/cm². The coercive field (2E_c) value of the SPBTN film was 102 kV/cm, which was much lower than that of SBTN (165 kV/cm). The effects of substitution on structural and ferroelectric properties of SBT were discussed in detail. As a result, the A- and B-sites co-substitution may be one of the promising ways to improve ferroelectric properties of SBT.     

Enhanced spontaneous polarization in Sr and Ca co-doped BaTiO3 ceramics

The dielectric and ferroelectric properties of (Ba_xSr_1−x)_0.77Ca_0.23TiO₃ ceramics with x=1 to 0.7 were studied and compared with those of Ba_xSr_1−xTiO₃ and Ba_0.77Ca_0.23TiO₃ ceramics. It has been found that Sr doping of the Ba_0.77Ca_0.23TiO₃ ceramics causes a drastic decrease of the Curie temperature, just like Sr doping of pure BaTiO₃ ceramics, demonstrating a cell volume effect. However, the (Ba_xSr_1−x)_0.77Ca_0.23TiO₃ ceramics with x=0.9 and 0.8 have larger spontaneous polarization than those of the corresponding Ba_xSr_1−xTiO₃ and Ba_0.77Ca_0.23TiO₃ ceramics, along with sufficient insulating properties. The enhancement of their polarization was explained by the increase of the lattice parameter c/a ratio due to the lattice distortion and strain developed in the ceramics.     

Polarized Micro-Raman Study of the Temperature-Induced Phase Transition In 0.67 Pb（Mg1/3Nb2/3）O3-0.33PbTiO3

Polarized Raman spectra of ferroelectric relaxor 0.67Pb（Mg1/3Nb2/3）O3-0.33PbTiO3 （0.67PMN-0.33PT） single crystal are systematically investigated in a wide temperature range from -196 to 600℃ by micro-Raman scattering technique. The results clearly reveal that there are two structural phase transitions in such composite ferroelectric relaxor： the rhombohedral-tetragonal （R- T） phase transition and the tetragonal-cubic （T- C） phase transition. The former occurs at about TR-T =34℃, corresponding to the vanishing of the soft A1 mode at 106cm^-1 recorded in the parallel polarization. The latter appears at about TT-C = 144℃, which can be verified with the vanishing of mode at 780cm^-1 measured in the crossed polarization.     

Raman study of phase transitions in KNbO3

The influence of grain size on the phase transitions of ferroelectric KNbO₃ was studied by micro Raman spectroscopy. It was found that the three transitions observed are not sharp for small particles (∼50 μm), indicating that they do not behave like bulk particles. The transition temperatures depend on the size and all particles show hysteresis. From these experiments we have obtained some evidence that in small particles monodomains of the rhombohedral and orthorhombic phases coexist in a range of temperatures.     

Field-Induced Domain Reorientation and Polarization Rotation of <110> Oriented Pb(Mg1/3Nb2/3)O3-PbTiO3 Single Crystals

Polarization hysteresis loops, x-ray diffraction and temperature dependent dielectric constant under different electric fields for <110> oriented 0.7PMN-0.3PT crystals are measured. The field-induced phase transition and the process of depolarization are discussed. The results show that with the electric field E increasing, the single-crystal form changes from the relaxor state of rhombohedral to normal rhombohedral, then to a monoclinic state via polar-axis reorientation and polarization rotation. Orthorhombic phase may present when E≥10kV, but it is an unstable form after E removal. The depolarization process is not just the reversal of the polarization process. It is noticed that only the temperature-dependent dielectric behaviour is not enough to judge the processes of the E-field induced phase transition.