Effect of electric field on electrocaloric effect in Pb(Zr1 − xTix)O3 solid solution

A thermodynamic analysis is employed to investigate the intrinsic electrocaloric effect of Pb(Zr_1 − xTi_x)O₃ solid solution system under the different electric field. Theoretical analysis indicates that Pb(Zr_1 − xTi_x)O₃ system has the giant electrocaloric coefficient and the large adiabatic temperature change near its ferroelectric Curie temperature. The applied electric field decreases not only the electrocaloric coefficient but also its temperature dependence. Furthermore, it increases the adiabatic temperature change as well as its dependence of temperature. The temperature corresponding to the maximum of electrocaloric coefficient and adiabatic temperature change increases with the enhancement of electric field because of its first-order phase transition between ferroelectric phase and paraelectric phase.     

A compositional fluctuation and properties of Pb(Zr,Ti)O3

Structure and properties of piezoelectric materials of composition Pb(Zr_xTi_1?x)O₃ near the morphotropic phase boundary between tetragonal and rhombohedral phases are studied. When these materials were prepared by a new “wet-dry combination technique”, no coexistence of these two phases was found in any range of compositions. This fact is in contrast with the case of Pb(Zr_xTi_1?x)O₃ prepared by an ordinary dry method. The coexistence behavior is interpreted in terms of compositional fluctuation, on the basis of which various properties of the materials are explained.     

Dielectric properties of lead zirconate titanate films synthesized through oxidation of metal layers

Films of the composition Pb(Zr _x Ti_1?x )O₃ are prepared by magnetron sputtering of metal layers onto titanium substrates with subsequent heat treatment in an oxygen atmosphere. The electrical properties of the samples prepared are investigated using impedance spectroscopy in the frequency range from 10² to 5 × 10⁵ Hz at temperatures of 300–750 K. The temperature dependences of the permittivity and the dielectric loss tangent at different frequencies exhibit a behavior typical of ferroelectrics and indicate the occurrence of a ferroelectric phase transition at temperatures close to T = 663 K. Analysis of the imaginary part of the electric modulus has revealed two possible relaxation mechanisms. The activation energy for dc electrical conduction in the paraelectric phase is determined.     

Phase coexistence in lead zirconate titanate solid solutions

This paper discusses the phenomena observed in the vicinity of the morphotropic phase boundary in Pb(Ti_1?x Zr_x)O₃ (PZT) solid solutions. The location of the boundary between the stable tetragonal ferroelectric phase and the stable rhombohedral ferroelectric phase is calculated, and an analytical expression for determining the concentration range of the possible coexistence of these phases is derived. According to the numerical estimates, the concentration range can be as much as 20 mol % lead zirconate. However, reliable experimental data in support of these estimates are as yet unavailable.     

In situ hot-stage transmission electron microscopy of Pb(Zr0.52Ti0.48)O3

The domain structure of Pb(Zr_0.52Ti_0.48)O₃ before and after hot-stage experiment has been studied. The influence of maximum temperature, heating and cooling rate on the domain configuration of Pb(Zr_{1? x} , Ti _x )O₃ with x = 0.40, 0.45, 0.48 and 0.55 was analysed. A reliable basis for further hot-stage experiments of Pb(Zr_1?x, Ti_x)O₃ has been established. The investigations revealed a temperature dependent appearance and disappearance of nano- and microdomains. The appearance of microdomains in the nano scale range during cooling, denoted as domain miniaturisation, and the time dependent recovering of the former domain structure, revealed that under specific experimental conditions the domain configuration is reversible.     

Piezoelectric activities and domain patterns of orthorhombic Ba(Zr,Ti)O3 ceramics

Ba(Zr_xTi_1?x)O₃ (0.025 ≤ x ≤ 0.065) ceramics were prepared by conventional solid-state reaction method. Crystalline structures were analyzed by X-ray diffraction. It was shown that all the Ba(Zr_xTi_1?x)O₃ (0.025 ≤ x ≤ 0.065) ceramics were of orthorhombic phase at room temperature. Piezoelectric activities and domain patterns were investigated and compared with those of BaTiO₃ ceramic. All the Ba(Zr_xTi_1?x)O₃ ceramics showed nearly the same d₃₃ values of about 265 pC/N and the same domain width of about 220 nm. By comparing the grain sizes and domain width of the Ba(Zr_xTi_1?x)O₃ ceramics with those of BaTiO₃ ceramic, it is speculated that the variation of domain width with grain sizes in orthorhombic Ba(Zr_xTi_1?x)O₃ ceramics may be different with that in tetragonal BaTiO₃ ceramic. Besides domain width, the effective inertia mass of domain wall is also considered to be a very important factor that impacts the piezoelectric activities of the Ba(Zr_xTi_1?x)O₃ ceramics.     

Antihysteresis of the electrical resistivity of graphene on a ferroelectric Pb(Zr x Ti1 − x )O3 substrate

A quantitative model is developed to explain the antihysteretic behavior of the electrical resistivity of graphene on a ferroelectric Pb(Zr _x Ti_{1 ? x} )O₃ substrate as a function of the gate voltage. The model takes into account the trapping of the electrons from the graphene layer by the states related to the graphene-ferroelectric interface. The finite energy gap of impurity states is also taken into account, which makes it possible to describe the well-known experimental dependences, including an increase and the subsequent saturation of a “memory window” with the switching gate voltage. The obtained estimates can be important for creating next-generation nonvolatile memory elements, which use the two stable values of electrical resistivity (one of them is attributed to logical “0” and the other, to “1”) that result from the antihysteresis effect.     

Low-temperature processing of sol–gel-derived lead–zirconate–titanate thin films by oxygen-plasma treatment

Ferroelectric thin films of sol–gel-derived Pb(Zr_x, Ti_1−x)O₃ (lead–zirconate–titanate, PZT) were obtained by the low-temperature processing employing oxygen-plasma treatment. The as-coated PZT films were annealed in oxygen ambience at 450 °C, followed by oxygen-plasma treatment at 200 °C, which gave rise to the ferroelectric hysteresis. Annealing of the as-coated PZT films followed by oxygen-plasma teratment at 200 °C gave rise to the ferroelectric hysteresis.     

‘Soft’ optical phonons and the morphotropic phase transition of the Pb(Ti1−x, Zrx)O3 system

Room temperature Raman scattering results for the Pb(Ti_1?x, Zr_x)O₃ system in its tetragonal ferroelectric phase are analyzed. For x ≤ 0.25, the square of the frequency of the ‘soft’ E(TO) phonon is linear in the Zr concentration. In addition, we find that the morphotropic phase transition at x = 0.535 may be associated with an instability of this ‘soft’ phonon. It is shown that changes in the short-range harmonic forces play an important role in the x-dependence of the ‘soft’ E(TO) phonon frequency.     

Ferroelectric properties of Pb(Zr1/2Ti1/2)O3–Pb(Zn1/3Nb2/3)O3 ceramics under compressive stress

Effects of compressive stress on the ferroelectric properties of ceramics in PZT–PZN system were investigated. The ceramics with a formula (1−x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Zn_1/3Nb_2/3)O₃ or (1−x)PZT–(x)PZN (x = 0.1–0.5) were prepared by a conventional mixed-oxide method. The ferroelectric properties under the compressive stress of the PZT–PZN ceramics were observed at the stress levels up to 170 MPa using a compressometer in conjunction with a modified Sawyer–Tower circuit. It was found that with increasing compressive stress the area of the ferroelectric hysteresis (P–E) loops, the saturation polarization (P_sat), the remnant polarization (P_r), and the coercive field (E_c) decreased. These results were interpreted through the non-180° ferroelastic domain switching processes.     

Effect of the Sintering Temperature on the Formation of Ferroelectric Properties of a Lead Zirconate–Titanate Ceramic

Effect of the sintering temperature on the formation of the microstructure, the domain structure, and the ferroelectric properties of a lead zirconate–titanate Pb(Ti _x Zr_{1 – x})O₃ piezoelectric ceramics has been studied. It is shown that the ferroelectric phase forms at a sintering temperature of 860°C. At higher sintering temperatures, the main effect on the properties is due to a unit cell deformation and free charge carriers.     

1/<Emphasis Type="Italic">E</Emphasis><Superscript>2</Superscript> Law: Solution of the Unsolved Problem in the Physics of Ferroelectrics

An unusual frequency dependence of a coercive field observed in polycrystalline ferroelectric films of Pb(Zr_{1 ? x}Ti_x)O₃ solid solutions in a wide frequency range has been explained within the model of surface sources emitting thin ferroelectric domains with reversed polarization. This model makes it possible to interpret experimental data as the manifestation of the coercivity paradox in polycrystalline films and predicts the existence of the limiting frequency for switching of domains in agreement with the experiment. The proposed mechanism of polarization switching explains the observed temperature dependence of the activation field E_a ∝ T^?1/2. Furthermore, it predicts an increase in the activation energy for the nucleation of domains with an increase in the size of the source, indicating that the coercive field increases with the degradation of small     

Synthesis and physicochemical properties of Li2 Me x Zr1 − x O3 − δ (Me = Nb,Ti; x = 0.05, 0.1) solid solutions

Complex lithium metallates Li₂ Me _x Zr_{1 ? x} O_{3 ? δ} (Me = Nb, Ti, x = 0.05, 0.1) with iso-and heterovalent substitutions for Zr⁴⁺ ions in lithium zirconate are synthesized for the first time using a citrate technique. The inclusion of Ti⁴⁺ and Nb⁵⁺ ions in the crystal structure of Li₂ZrO₃ is confirmed by means of X-ray diffraction and NMR. It is shown that in the temperature range of 750–820 K, Li₂Ti_0.1Zr_0.9O₃ solid solution has higher conductivity than phases of undoped lithium zirconate.     

Synthesis of Zr-doped TiO2 templated from cloth and its photocatalytic activity

Biomorphic Zr-doped TiO₂ (Zr _x Ti_{1 ? x} O₂) with hierarchical micro- and nanostructures was successfully fabricated using cloth as the host template. We found that the resulting Zr _x Ti_{1 ? x} O₂ faithfully duplicated the morphologic microstructures of the initial cloth with grain size of about 10–50 nm. The photocatalytic activity of the as-prepared Zr _x Ti_{1 ? x} O₂ was examined by the degradation of rhodamine B in aqueous solution under simulated solar light, which showed that templates pretreated with NaOH solution followed by mixed acid and an appropriate amount of doped Zr (3 mol%) could significantly enhance the photocatalytic activities of Zr _x Ti_{1 ? x} O₂. This simple template method provides a cost-effective and ecofriendly route to synthesize other metal-doped semiconductor materials of predicted morphology.     

Shape memory effect in PZST system at exact morphotropic phase boundary

Unmodified lead zirconate titanate stannate (PZST) system with compositional formula Pb [(Zr_0.7Sn_0.3)_xTi_(1−x)]O₃, where 0.92≤x≤0.94 has been studied at Morphotropic phase boundary (MPB) for dielectric, ferroelectric and shape memory effect. Field-induced strain measurements are presented to show that ∼0.08% remnant strain pertaining to shape memory can be observed in PZST ceramics at near-exact MPB.     

Crystallization kinetics and growth mechanism of Pb(Zr0.52·Ti0.48)O3 nanopowders

In this study, Pb(Zr_0.52·Ti_0.48)O₃ nanopowders were synthesized via sol–gel process. Particle morphology, crystalline phases and thermal behavior were characterized by scanning electron microscopy, X-ray diffraction and simultaneous thermal analyzer, respectively. The X-ray diffraction pattern showed perovskite phase clearly. The non-isothermal activation energy for the perovskite crystallization in Pb(Zr_0.52·Ti_0.48)O₃ gel powders was 224.91 kJ mol^?1. Both growth morphology parameter (n) and crystallization mechanism index (m) are close to 3.0, indicating that the bulk nucleation is dominant in the perovskite PZT formation. To determine dielectric properties, the calcined Pb(Zr_0.52·Ti_0.48)O₃ nanopowders were pressed using uniaxial press. It was found that the Pb(Zr_0.52·Ti_0.48)O₃ disks, by sintering at 1,200 °C for 2 and 10 h, and at 1 kHz frequency, had 966 and 1,490 of the dielectric constant, respectively.     

Development of perovskite and phase transition in lead cobalt niobate modified lead zirconate titanate system

Ferroelectric lead zirconate titanate–lead cobalt niobate ceramics with the formula (1 − x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Co_1/3Nb_2/3)O₃ where x = 0.0–0.5 were fabricated using a high temperature solid-state reaction method. The formation process, the structure and homogeneity of the obtained powders have been investigated by X-ray diffraction method as well as the simultaneous thermal analysis of both differential thermal analysis (DTA) and thermogravimetry analysis (TGA). It was observed that for the binary system (1 − x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Co_1/3Nb_2/3)O₃, the change in the calcination temperature is approximately linear with respect to the PCoN content in the range x = 0.0–0.5. In addition, X-ray diffraction indicated a phase transformation from a tetragonal to a pseudo-cubic phase when the fraction of PCoN was increased. The dielectric permittivity is remarkably increased by increasing PCoN concentration. The maximum value of remnant polarization P_r (25.3 μC/cm²) was obtained for the 0.5PZT–0.5PCoN ceramic.     

Index of refraction in ‘dirty’ displacive ferroelectrics

We report measurements of the optic index of reflection as a function of temperature, n(T), for several highly disordered ferroelectrics: PLZT ceramic [Pb_1?xLa_x(Zr_0.65Ti_0.35)_1?x/4O₃ where x = 0.08] and single crystals of Pb₃(MNb₂)O₉ where M = Zn and Mg. The results are qualitatively different from the unusual displacive ferroelectric behavior and the difference is clearly due to local disorder.     

Dielectric and pyroelectric activities in Pb(Zr1−xTix)O3 ceramics: The role of the phase transition effects

Pure and Nb-doped Pb(Zr_1−xTi_x)O₃ (x = 0.47, 0.48, 0.50) ceramics were prepared by conventional solid-state reaction technique. Dielectric anomalies are observed in both kinds of samples near room temperature. The anomalies could be depressed by donor doping and prefer to be significant in ceramics with tetragonal crystallographic phase. Phase transition mechanism and domain wall pinning effect are proposed to explain this anomaly, and the former is considered as the dominated reason. Further results of the pyroelectric measurements confirm the existence of the ferroelectric–ferroelectric phase transition.     

Comparative study of solid-state reaction and sol-gel process for synthesis of Zr-doped Li<Subscript>0.5</Subscript>La<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> solid electrolytes

We investigated the synergistic influences of synthesis methods (solid-state reaction vs. sol-gel process) and Zr⁴⁺ doping on the structure and ionic conductivity of perovskite-structured Li_0.5La_0.5TiO₃ (LLTO) solid electrolytes. The lithium-ion conductivity of Li_0.5La_0.5Ti_1???x Zr _x O₃ ceramic specimens was evaluated as a function of x value and compared carefully between those two synthesis methods. Regarding the conductivity, sol-gel process is better for the synthesis of LLTO than solid-state reaction. As a result, the highest grain conductivity is obtained in the sol-gel-derived pure LLTO sample with x?=?0, reaching 1.10?×?10^?3 S?·?cm^?1. Partial substitution of Zr⁴⁺ enlarges the LLTO’s grain aggregate size and increases the total superficial area of aggregates. Consequently, Zr⁴⁺ substitution not only affects the grain (bulk) conductivity, but more importantly, also improves the grain boundary conductivity and the total conductivity. The highest total conductivity is 5.84?×?10^?5 S?·?cm^?1 with x?=?0.04 by sol-gel process.