Phase transition and linear thermal expansion of (Pb1− x Ba x )ZrO3 ceramics

(Pb_{1? x} Ba _x )ZrO₃ ceramics for the composition range 0?≤?x?≤?0.30 were prepared by the mixed oxide solid state reaction method. Phase transition was studied by dielectric and dilatometric measurements. The ferroelectric to paraelectric phase transition temperature was progressively shifted to a lower temperature by replacing lead with barium. The x?=?0.20 sample showed the maximum dielectric constant of 16,300 at the transition temperature. For compositions 0?≤?x?≤?0.075, the antiferroelectric to ferroelectric phase transition exhibited a large linear thermal expansion. However, the antiferroelectric to ferroelectric phase transition did not exist for 0.10?≤?x?≤?0.30 samples. A phase diagram for PBZ ceramics prepared by the conventional mixed oxide method was also present.     

Description of ferroelectric phase transitions in solid solutions of relaxors in the framework of the random-field theory

A model based on the random-field theory is proposed for calculating the properties of solid solutions of ferroelectric relaxors. The electric dipoles randomly distributed in the system are treated as sources of random fields. The random field distribution function is calculated taking into account the contribution of nonlinear and correlation effects and the differences in the dipole orientations for different solid solution components. The dependence of the phase transition temperature T _c on the concentration of solid solution components is analyzed. Numerical calculations are performed for the lead scandoniobate and lead scandotantalate solid solutions (PbSc_1/2Nb_1/2O₃)_1?x (PbSc_1/2Ta_1/2O₃)_x with different degrees of ordering and the lead magnoniobate and lead titanate solid solution (PbMg_1/3Nb_2/3O₃)_1?x (PbTiO₃)_x. It is shown that the higher transition temperature for more disordered solid solutions of the composition (PbSc_1/2Nb_1/2O₃)_1?x (PbSc_1/2Ta_1/2O₃)_x in the range 0≤x<0.5 is associated with the larger nonlinearity coefficient for PbSc_1/2Nb_1/2O₃ as compared to that for PbSc_1/2Ta_1/2O₃. The theory provides a means for calculating the region of the coexistence of the phases with different symmetry groups in the temperature-composition phase diagram of the (PbMg_1/3Nb_2/3O₃)_1?x (PbTiO₃) solid solution. Numerical calculations with the use of the fitting parameters obtained from the known transition temperatures T _c for the solid solution components adequately describe the experimental phase diagrams for the aforementioned solid solutions of ferroelectric relaxors.     

Control of the temperature hysteresis and diffuse dielectric anomaly in the temperature range of the ferroelectric-antiferroelectric phase transition in PbZr1 − x TixO3 (0.03 ≤ x ≤ 0.05) ceramics

The magnitudes of the temperature hysteresis and diffuse dielectric anomaly corresponding to the transition from the antiferroelectric phase to the ferroelectric phase in PbZr_{1 ? x} Ti_xO₃ (0.03 ≤ x ≤ 0.05) ceramics can be reversibly changed by varying the temperatures of heating and cooling in the course of thermocycling. The results obtained indicate that the antiferroelectric-ferroelectric transition in the PbZr_{1 ? x} Ti_xO₃ ceramics materials is a smeared first-order phase transition.     

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.     

Ti-doping induced antiferroelectric to ferroelectric phase transition and electrical properties in Sm-PbZrO3 thin films

The antiferroelectric (Pb_0.985Sm_0.01) (Zr_1-xTi_x)O₃ (Ti-PSZO) thin films were synthesized on Pt(111)/Ti/SiO₂/Si substrates using a chemical solution deposition method. The films were crystallized in the perovskite phase with a preferential orientation along (111) direction. With Ti doping in PSZO, a gradual transformation from antiferroelectric to ferroelectric phase transition was noticed at room temperature owing to the Ti doping induced lattice distortion. The phase transition has been confirmed through the P - E hysteresis loops, X-ray diffraction (peak shifting), capacitance-voltage measurements, and Raman scattering analysis. The thin film with Ti = 0.15 doping displayed a ferroelectric behavior with high dielectric constant and large dielectric tunability of about 62%. Also, Ti doping altered the Curie temperature (T_c) and enhanced the order of dielectric diffuseness. It is believed that Ti-doping in PSZO is an effective way to induce an antiferroelectric - ferroelectric phase transition and to tailor the electrical characteristics of PSZO thin films.     

Phase coexistence in proton glass

Abstract

Proton glasses are crystals of composition M_1?x(NW₄)_xW₂A0₄, where M = K,Rb,Cs, W = H,D, A = P, As. For x = 0 there is a ferroelectric (FE) transition, while for x-1 there is an antiferroelectric (AFE) transition. In both cases, the transition is from a paraelectric (PE) state of tetragonal structure with dynamically disordered hydrogen bonds to an ordered state of orthorhombic structure. For an intermediate x range there is no transition, but the hydrogen rearrangements slow down, and eventually display nonergodic behavior characteristic of glasses. We and others have shown from spontaneous polarization, dielectric permittivity, nuclear magnetic resonance, and neutron diffraction experiments that for smaller x there is coexistence of ferroelectric and paraelectric phases, and for larger × there is coexistence of antiferroelectric and paraelectric phases. We present a method for analytically describing this coexistence, and the degree to which this coexistence is spatial and/or temporal. We discuss also the experimental determination of these coexistence parameters.     

Phase formation and dielectric phase transition in Ba1−xCaxTi0.6Zr0.4O3 solid solutions

Perovskite types Ba_1−xCa_xTi_0.6Zr_0.4O₃ (with x=0.0-0.5) ceramics have been prepared through solid state reaction route. The room temperature XRD study suggests the compositions with x=0.0 and x=0.1 have single phase cubic symmetry. With further increase in Ca content, solid solution breaks and an orthorhombic CaTiO₃ like phase is developed. The dielectric study on single phase compositions (x=0.0 and 0.1) reveals that the materials are of relaxor type and undergo a diffuse type ferroelectric phase transition. In the Ca containing composition higher transition temperature is observed than the pure BaTi_0.6Zr_0.4O₃ materials. In the paraelectric region (above T_c) lower diffusivity is observed in the Ca containing composition. The strength of relaxation is calculated and found to be more in Ca containing material than that of pure BaTi_0.6Zr_0.4O₃ composition.     

Antiferroelectric–ferroelectric phase transition in lead zinc niobate modified lead zirconate ceramics: crystal studies, microstructure, thermal and electrical properties

The combination of antiferroelectric PbZrO₃ (PZ) and relaxor ferroelectric Pb(Zn_1/3Nb_2/3)O₃ was prepared via the columbite precursor method. The basic characterizations were performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), linear thermal expansion, differential scanning calorimetry (DSC) techniques, dielectric spectroscopy, and hysteresis measurement. The XRD result indicated that the solid solubility limit of the (1−x)PZ–xPZN system was about x=0.40. The crystal structure of (1−x)PZ–xPZN transformed from orthorhombic to rhombohedral symmetry when the concentration of PZN was increased. A ferroelectric intermediate phase began to appear between the paraelectric and antiferroelectric phases of pure PZ, with increasing PZN content. In addition, the temperature range of the ferroelectric phase increased with increasing PZN concentration. The morphotropic phase boundary (MPB) in this system was located close to the composition, x=0.20.     

Ferroelectric phase transitions in ionic conductors based on bismuth vadanate

Ceramic solid solutions (Bi_{1 ? x} La _x )₄V₂O_{11 ? z} (I), Bi₄(V_{1 ? x} Fe _x )₂O_{11 ? y} (II), and (Bi_{1 ? x} La _x )₄(V_0.96Fe_0.04)₂O_{11 ? y} (III) (x = 0–0.3, step Δx = 0.02) are prepared using solid-phase synthesis. The concentration and temperature ranges of stabilization of different polymorphic modifications, including the ranges of concentrations x corresponding to the stabilization of the ferroelectric phase, are established. It is revealed that an increase in the concentration x in the region of existence of the pseudoorthorhombic phase α of the solid solutions studied leads to a decrease in the transition temperature, smearing of the transition, and an increase in the width of the thermal hysteresis of the ferroelectric phase transition. The effect of compressing of the domain walls by oxygen vacancies was revealed in the samples from the region of existence of the ferroelectric α phase, and the effect of dielectric relaxation was detected in the samples from the region of existence of the orthorhombic phase β.     

Ab initio calculation of the ferroelectric phase transition in disordered and ordered PbSc0.5Ta0.5O3 and PbSc0.5Nd0.5O3 solid solutions with the use of a model Hamiltonian

To describe the ferroelectric phase transition in ordered and disordered PbSc_0.5Ta_0.5O₃ (PST) and PbSc_0.5Nd_0.5O₃ (PSN) solid solutions, a model Hamiltonian is written in the local-mode approximation, in which long-range dipole-dipole and short-range interactions of local modes are taken into account. The Hamiltonian parameters are determined from the set of energies of a series of distorted structures, calculated within the nonempirical generalized Gordon-Kim model. The statistical mechanics of the systems with a model Hamiltonian is investigated by the Monte Carlo method. It is revealed that PSN solid solutions undergo a transition to the ferroelectric rhombohedral phase through an intermediate phase, existing in a narrow temperature range. PST solid solutions undergo a ferroelectric phase transition directly from the paraelectric cubic to the ferroelectric rhombohedral phase. Original Russian Text ? V.I. Zinenko, N.G. Zamkova, 2008, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2008, Vol. 133, No. 3, pp. 622–631.     

Concentration-phase transitions in solid solutions Li x Na1 − x Ta0.1Nb0.9O3, Li0.12Na0.88Ta y Nb1 − y O3, and NaTa y Nb1 − y O3 and their manifestations in Raman spectra

Using the Raman-spectroscopy method, we have studied concentration-phase transitions in the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃, Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ (x = 0?0.16, y = 0–1). It has been revealed that, for the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃ and Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, the concentration-phase transition is a transition between the ferroelectric and antiferroelectric states. It is accompanied by the disappearance from the spectrum of a line that corresponds to stretching bridge vibrations of oxygen atoms along the polar axis, which is forbidden by selection rules in the centrosymmetric phase, and by splitting into two components of a line that corresponds to librational vibrations of oxygen octahedra as a whole, which can be caused by doubling of the unit cell in the antiferroelectric phase. Manifestation and variation of intensities of lines with frequencies 860–873 and 900–905 cm^?1 upon variation of the concentration of tantalum for solid solutions Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ is caused by the formation of polar clusters in the medium, which is centrosymmetric in general due to disordering in the sublattice of niobium and tantalum.     

Investigation of the ferroelectric–relaxor crossover in Ce-doped BaTiO3 ceramics by impedance spectroscopy and Raman study

BaCe _x Ti_{1? x} O₃ (x?=?0.06, 0.10, and 0.20) solid solutions were prepared via conventional the solid-state reaction and sintered at 1500°C for 4?h, resulting in dense single phase ceramics with homogeneous microstructures. The electric field dependence of permittivity of the BaCe _x Ti_{1? x} O₃ ceramics was investigated in detail, together with the ferroelectric–paraelectric phase transition features. A transformation from normal to relaxor ferroelectrics was observed by increasing the Ce concentration. For low-Ce content, a substitution of Ce on both A and B site positions was proposed from the dielectric study and confirmed by Raman analysis.     

Li and Nb codoping in dielectric properties and phase transitions of KTaO3: Reentrant dipolar glass and long-range dipole ordering

Abstract

The highly polarizable perovskite-type oxide, KTaO₃ doped simultaneously with Li⁺ and Nb⁵⁺ (K_1?xLi_xTa_1?yNb_yO₃, KLTN), reveals unexpected properties and ordering effects. Studies of the dielectric permittivity ?'(T, f) (10—300K, 100Hz-1 MHz) for x = 0.0014 and y = 0.024 show collective dipolar ordering effects with a transition from paraelectric into a mixed phase (coexisting dipole-glass-like and long-range ordered ferroelectric phases) taking place near 39 K. At 15 K another phase transition into a reentrant dipolar glass-like state is observed. Such a sequence of transitions and the existence of a reentrant glass state are unknown for electrical dipolar systems.     

Role of Mn doping for obtaining of hexagonal phase in Ba0.98Zn0.02TiO3 ceramics

This paper reports the observation of hexagonal phase of barium titanate by Mn doping and its effect on dielectric and magnetic properties. Ceramic samples of Ba_0.98Zn_0.02Ti_1−xMn_xO₃ (where, x= 0.04, 0.06 and 0.08) were prepared by traditional solid-state reaction route. The hexagonal phase is stabilized in the composition Ba_0.98Zn_0.02Ti_0.92Mn_0.08O₃ and a very feeble M–H loop is also observed in that composition. This induced magnetism is expected due to the exchange interactions between magnetic polarons formed by oxygen vacancies with Mn ions. The dielectric constant as well as the ferroelectric to paraelectric transition temperature is systematically decreased with increasing of Mn doping concentration. Further to that, the temperature dependent dielectric constant curve is also broadened at transition temperature with increasing of Mn concentration. However, the ferroelectric to paraelectric transition temperature is well above room temperature.     

Ferroelectric phase stabilization, phase transformations and?thermal properties in (1? x )PbZrO3– x Pb(Co1/3Nb2/3)O3 solid solution

The solid solution between the antiferroelectric PbZrO₃ (PZ) and relaxor ferroelectric Pb(Co_1/3Nb_2/3)O₃ (PCoN) was synthesized by the columbite method. The phase structure and thermal properties of (1−x)PZ–xPCoN, where x=0.0–0.3, were investigated. With these data, the ferroelectric phase diagram between PZ and PCoN has been established. The crystal structure data obtained from XRD indicates that the solid solution PZ–PCoN, where x=0.0–0.3, successively transforms from orthorhombic to rhombohedral symmetry with an increase in PCoN concentration. The AFE→FE phase transition was found in the compositions of 0.0≤x≤0.10. The AFE→FE phase transition shift to lower temperatures with higher compositions of x. The width of the temperature range of FE phase was increased with increasing amount of PCoN. It is apparent that the replacement of the Zr⁴⁺ ion by (Co_1/3Nb_2/3)⁴⁺ ions would decrease the driving force for antiparallel shift of Pb²⁺ ions, because they interrupt the translational symmetry. This interruption caused the appearance of a rhombohedral ferroelectric phase when the amount of PCoN was more than 10 mol%.     

Microstructure and piezoelectric properties of Bi0.5(Na0.82K0.18)0.5TiO3−NaSbO3 ceramics

Lead-free piezoelectric ceramics (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ have been prepared by a conventional ceramics technique, and their microstructure and electrical properties have been investigated. The addition of NaSbO₃ has no remarkable effect on the crystal structure within the studied doping content; however, an obvious change in microstructure took place. With increase in NaSbO₃ content, the temperature from a ferroelectric to antiferroelectric phase transition increases, and the temperature for a transition from antiferroelectric phases to paraelectric phases changes insignificantly. Simultaneously, the temperature range between the rhombohedral phase transition point and the Curie temperature point becomes smaller. The piezoelectric properties significantly increase with increase in NaSbO₃ content and the piezoelectric constant and electromechanical coupling factor attain maximum values of d₃₃=160 pC/N and k_p=0.333 at x=0.01. The results indicate that (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ ceramic is a promising lead-free piezoelectric candidate material.     

Phase transitions in xPbZr0.53Ti0.47O3-(1 − x)Mn0.4Zn0.6Fe2O4 magnetoelectric composites

The elastic, inelastic, and dielectric properties of the magnetoelectric composite xPbZr_0.53Ti_0.47O₃-(1 ? x)Mn_0.4Zn_0.6Fe₂O₄ (PZT-MZF) are studied in the temperature range from room temperature to 673 K. The influence of the ferroelectric PZT phase on the magnetic phase transition and the magnetic MZF phase on the ferroelectric phase transition is revealed. It is established that, as the PZT content increases, the degree of diffuseness of the phase transition decreases and a gradual crossover from a pronounced relaxor behavior to a more ordered ferroelectric behavior occurs.     

Differential thermal analysis of phase transitions in (Bi1−xLax)FeO3 solid solution

(Bi_1?xLa_x)FeO₃ solid solution, a material exhibiting simultaneously electric and magnetic long range dipole order, is studied by the method of differential thermal analysis. The results confirm the data on ferroelectric phase transitions obtained from electric permittivity and dilatometric measurements above 500°C. The endothermal effect observed about 820°C is related to the ferroelectric phase transition of BiFeO₃.     

Lattice dynamics, ferroelectric and antiferroeelctric instabilities, and the ferroelectric phase transition in disordered PbB′1/2B″1/2O3 (B′ = Ga, In, Lu; B″ = Nb, Ta) solid solutions

The lattice vibration spectra, rf permittivity, and dynamic Born charges of disordered PbB′_1/2B″_1/2O₃ (B′ = Ga, In, Lu; B″ = Nb, Ta) solid solutions are calculated in terms of the generalized Gordon-Kim model. All the compounds are found to have soft modes related to the center (Γ₁₅) and boundary point R (R ₁₅) of the Brillouin zone; the frequencies of these modes are close. The ferroelectric phase transition temperatures and the spontaneous polarization in the ferroelectric phase are calculated for the solid solutions using a model Hamiltonian in the local mode approximation and the Monte Carlo method. These temperatures for the tantalum compounds are found to be higher than for the niobium compounds, and temperature t _s increases with the atomic number of ion B′. A model where the antiferroelectric state is related to the condensation of modes Γ₁₅ and R ₁₅ is proposed. It is found that, for all compounds except for PbSc_1/2Nb_1/2O₃ and PbSc_1/2Ta_1/2O₃, the ferroelectric phase, which is only related to the condensation of mode R ₁₅, and the antiferroelectric phase have similar energies. In PbIn_1/2Ta_1/2O₃, the antiferroelectric phase turns out to be energetically favorable.     

Successive phase transitions in the highly ordered complex perovskite PbLu1/2Nb1/2O3

The structural phase transitions and the electrical behaviour of the complex perovskite PbLu_1/2Nb_1/2O₃ have been investigated using X-ray powder diffraction, dielectric constant measurements, differential scanning calorimetry and measurement of the polarisation as a function of applied electric field. The high-temperature paraelectric phase is highly ordered. A first-order paraelectric-antiferroelectric phase transition occurs at 270°C and an antiferroelectric-ferroelectric phase transition, characterised by dispersion in the curves of dielectric constant as a function of temperature, occurs at ≈ 30°C. The antiferroelectric phase is isostructural with the orthorhombic form of PbYb1/₂Nb1/₂O₃. The low-temperature ferroelectric phase also has an orthorhombic crystal structure.