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.     

Fluctuations and Landau-Devonshire expansion for barium titanate

The experimentally observed temperature dependence of the quartic coefficients in the Landau-Devonshire expansion for BaTiO₃ is naturally accounted for within a proper fluctuation model. It is explained, in particular, why one of the quartic coefficients varies with temperature above T _c , while the second is constant. It is argued that the tetragonal phase in BaTiO₃ exists essentially due to thermal fluctuations, while the true Landau-Devonshire expansion with temperature-independent coefficients favors the rhombohedral ferroelectric phase.     

Landau behaviour of the heat capacity of AgNa(NO2)2 close to the nearly tricritical ferroelectric phase transition

The heat capacity of a single crystal of the uniaxial ferroelectric AgNa(NO₂)₂ was measured close to the nearly tricritical phase transition. In the ferroelectric phase a strong temperature dependence of the anomaleous specific heat is found which obeys a temperature law (θ _f —T)^?0.494. A small latent heat was detected nearT _c. The thermal behaviour of AgNa(NO₂)₂ is described by a Landau type theory, from which the non linear coefficientsζ andζ of the free energy expansion are derived. The thermal data fit well to the known dielectric behaviour.     

Dielectric,structural and specific heat properties of lead-free [(1−x)(Na0.5Bi0.5)−xBa]Zr1−yTiyO3 ceramics (x = 0.06, 0.085, 0.09, 0.1 and y = 0.97)

Lead-free [(1?x)(Na_0.5Bi_0.5)?xBa]Zr_1?yTi_yO₃ ceramics (x = 0.06, 0.085, 0.09, 0.1 and y = 0.97) have been prepared by solid-state hot-pressing sintering process. The obtained samples reveal perovskite structure. Structural, thermal expansion, heat capacity, ferroelectric and dielectric measurements have been carried out on these samples in a wide temperature range. The broad anomalies were observed in thermal expansion and heat capacity, which approximately correspond to a structural, ferroelectric and dielectric properties anomaly. These anomalies can be related to temperature features of polar regions and a formation of long-range-order ferroelectric phase. The determined Burns temperature was found to increase with increasing Ba content. The obtained results are discussed in terms of local electric and strain fields caused by a difference in the ionic radii of (Na,Bi) and Ba, and Ti and Zr ions. The NBT–BTZ system is expected to be a new promising candidate for lead-free electronic ceramics.     

Dielectric properties of porous aluminum and silicon oxides with inclusions of triglycine sulfate and its modified analogs

This paper reports on an investigation of the temperature dependences of the capacitance and conductance of composite materials prepared by incorporating the ferroelectric TGS and its analogs—TGS with addition of L,α-alanine and chromium—into porous Al₂O₃ and SiO₂ matrices. It has been established that conduction of the structures under study involves charge transport predominantly through the ferroelectric embedded in the porous matrix. A mechanism is proposed to account for the displacement of the phase transition temperature of the ferroelectric inclusion under “restricted geometry” conditions, which is driven by the difference between the thermal expansion coefficients of the porous matrix and the embedded ferroelectric.     

Phase-matched second-harmonic generation due to thermal expansion of TlGaSe2 layered crystal

Second-harmonic generation effects have been investigated in TlGaSe₂ layered crystal over a temperature range where ferroelectric phase exists. Pronounced periodical changes of the second-harmonic signal with temperature have been discovered. The observed effect is explained within the phase synchronism condition which changes with the temperature. The main mechanism of the thermal expansion of the sample in the observed phenomenon is explained.     

Thermal expansion of the Sn2P2(Se0.28S0.72)6 solid solutions

In the present work, we have experimentally studied and analysed the dilatometric properties of Sn₂P₂(Se_0.28S_0.72)₆ crystals during ferroelectric phase transition. A complete matrix of thermal expansion tensors as well as the characteristic surface of the thermal expansion tensor has been obtained. The critical exponent for the volume thermal expansion coefficient in Sn₂P₂(Se_0.28S_0.72)₆ crystals has been determined to be equal to 0.50 ± 0.06, which is peculiar to tricritical behaviour. Non-agreement in the values of the critical exponents evaluated from the temperature dependencies of relative elongation (0.17 ± 0.01) and volume thermal expansion coefficient (0.50 ± 0.06) is shown to be due to the possible temperature rotation of the spontaneous polarisation vector.     

Thermal expansion of Sn2P2S6 crystals

We present the results for thermal expansion coefficients of Sn₂P₂S₆ crystals determined both in the crystallographic system and the system based on eigenvectors of thermal expansion tensor. Peculiarities of temperature evolution of the indicative surface of thermal expansion tensor for Sn₂P₂S₆ are discussed, including the region of their ferroelectric phase transition.     

Specific features of the thermal physical properties of relaxor ceramics based on lead zirconate titanate

The heat capacity and thermal expansion of ferroelectric relaxors based on lead zirconate titanate are studied near the diffuse phase transition. It is shown that no spontaneous phase transitions from the paraelectric phase to the ferroelectric phase and from the relaxor state to the normal ferroelectric state occur in an ensemble of nanometer-sized polar regions. It is noted that the transitions can be caused only by external electric fields or storage for a fairly long time.     

Effects of composition ratio on structure and phase transition of ferroelectric nanocomposites from silicon dioxide nanoparticles and triglycine sulfate

The present work is devoted to study on influences of silicon dioxide nanoparticles (SiO₂) on structure and phase transition of a classical ferroelectric of triglycine sulfate (TGS) by synthesizing a composite containing SiO₂ and TGS at different composition weight ratios. Particle size analysis, X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR) techniques were utilized to charaterize the synthesized composite. The experiments for investigation of phase transition were conducted from 20 to 120°C under a weak electric field (1?V.cm^?1) at 1?kHz. The results revealed an expansion of ferroelectric phase of TGS by 15–55°C with increasing the SiO₂ content. Besides, an additional phase transition point which is characteristic for the bulk clusters of TGS was found at low content of SiO₂. The detected anomalies were discussed thoroughly based on the interaction between components in the composite.     

Symmetry breaking at the phase transitions in ferroelectric pyridinium salts

The phase transitions in ferroelectric pyridinium tetrafluoroborate (PyBF₄) and pyridinium perchlorate (PyClO₄) have been characterized by structural studies. The continuous ferroelectric phase transition at 238.7 K in PyBF₄ appears to be a unique case for multiaxial ferroelectrics, while the first order phase transition in PyClO₄ at 248 K is consistent with the Landau theorem for deducing the character of phase transitions from symmetry considerations. The phase transition in both materials is caused by ordering of the pyridinium cation as well as tetrahedral anions.     

Caloric characteristics of PbTiO3 in the temperature range of the ferroelectric phase transition

The heat capacity and thermal expansion of the PbTiO₃ ceramic sample have been measured in the temperature range 80?C970 K. The electrocaloric and barocaloric efficiencies of lead titanate in the ferroelectric phase transition range have been investigated by analyzing the experimental data in terms of the thermodynamic theory of phase transitions, the electrical equation of state P(T, E), the Pippard equation, and the S(T, p) diagram.     

On the low temperature phase transition in (NH4)2SO4

An ultracryostat and multidecameter were used to determine the temperature dependence of the dielectric constant ?′ and dielectric loss ?″ over a wide range of frequencies of single crystals and polycrystalline samples of (NH₄)₂SO₄ in the region of the low temperature phase transition. A sharp increase was observed in the values of ?′ and ?″ at about ?50°C. In addition, a dielectric dispersion was detected and found to be more pronounced in the high temperature phase. This dispersion was attributed to piezoelectric resonance. The observed sudden increase in the values of the dielectric constant and dielectric loss below ? 50°C was attributed to the ferroelectric nature of the low temperature phase of (NH₄)₂SO₄.A DTA thermogram showed a sharp peak at ? 50°C which indicated that the phase transition is one of first order type. A TMA thermogram showed that this transformation was associated with a rapid increase in the expansion coefficient. Such an increase in the lattice parameter might be attributed to the enhanced rotation of electric dipoles associated with the distorted NH₄⁺ and SO₄^2? ions. The distortion of both the ammonium and sulfate ions in addition to their expected orientational motion are suggested to be responsible for the ferroelectric behaviour of ammonium sulfate below ?50°C.A transition to a metastable hexagonal state at about ?40°C is thought to occur, and this transformation is found to be irreversible.     

Ferroelectricity associated with the metastable phase “III” of AgNO3

The dielectric constant, dc resistance, D-E ferroelectric hysteresis loop and dilatometric analysis of the three phases I, II, and III of AgNO₃ single crystals has been studied over the temperature range 100–200° C. A ferroelectric behaviour of the metastable phase III was detected here for the first time similar to what happened in KNO₃. The ferroelectric is attributed here to Ag⁺-ion vacancy formation in the unit cell of AgNO₃. The energy activating the process of vacancy formation was found to beE _v=2.6 eV. It was found that an ionic shift from one lattice point to another requires an amount of energy to overcome a potential barrierE _m=0.1 eV. A model is suggested to explain such behaviour. Dilatometric analysis indicated that this metastable phase transition III is accompanied by an expansion of the unit cell.     

Electret states and the phase transition in a surface layer of the TlGaSe2 ferroelectric semiconductor

The electret polarization is investigated in the TlGaSe₂ ferroelectric semiconductor. It is proved for the first time that stable internal electric fields associated with residual electret polarization are induced in crystals of the TlGaSe₂ ferroelectric semiconductor at temperatures T < 200 K. It is experimentally established that the peak of the pyroelectric current measured in the vicinity of the phase transition to the ferroelectric polar phase depends substantially on the temperature at which the external electric field is switched off when the TlGaSe₂ ferroelectric crystal under investigation is preliminarily cooled from room temperature. The results obtained are discussed in the framework of a model according to which internal electret fields are induced by charges localized at different levels in the bulk and on the surface of the TlGaSe₂ ferroelectric crystal. These fields drastically change at temperatures in a narrow range near 135 K. The inference is made that a phase transition occurs in the surface layer of the TlGaSe₂ crystal at a temperature close to ～135 K.     

Observation of ferroelectricity induced by defect dipoles in the strain-free epitaxial CaTiO3 thin film

CaTiO₃ is a well-known incipient ferroelectric material that does not undergo a ferroelectric phase transition in spite of the intriguing dielectric constant behavior. Especially, unlike a prototypical incipient ferroelectric SrTiO₃, the paraelectric state of CaTiO₃ cannot be easily destroyed by small perturbations, including cation doping and epitaxial strain. We present that a nearly strain-free epitaxial CaTiO₃ film grown at a low oxygen partial pressure exhibits polarization–voltage hysteresis loops and the distinct difference of piezoresponse force microscopy phase signals, implying that a ferroelectric phase is induced. Such results are shown even at room temperature. We suggest that the observed ferroelectric behavior in CaTiO₃ film comes from the defect dipoles composed of vacancies inside the film. Using electron-probe microanalysis and optical absorption spectra measurements, we found that CaTiO₃ film has considerable Ca and O vacancies, forming the localized defect state in electronic structure. This work highlights the importance of vacancies and their clusters, such as defect dipoles, in understanding the electronic properties of perovskite oxide thin films, including ferroelectricity.     

Thermal properties of PZT-based ferroelectric ceramics

The thermal properties of piezoelectric ceramics (PKR-8, PKR-7M) based on lead zirconate titanate solid solutions Pb(Ti, Zr)O₃ were studied over the temperature range 300–800 K. The thermal conductivity and thermal expansion coefficients were found to exhibit an anomalous behavior in the region of the ferroelectric phase transition.     

Observation of87Rb NMR satellite transitions in the commensurate and incommensurate phases of Rb2ZnCl4

It is shown that the first order quadrupole split NMR satellite transition frequencies of the⁸⁷Rb nucleus can be detected in the paraelectric, incommensurate and ferroelectric phases of Rb₂ZnCl₄. From rotation patterns the electric field gradient tensor at the Rb sites is determined for the paraelectric phase. The data demonstrate a considerable influence of the structural changes in the incommensurate and ferroelectric phases on the observed NMR transition frequencies. For some crystal orientations the satellite transitions are followed through the incommensurate into the ferroelectric phase. Whereas in the former typical quasi continuous spectra are observed in the latter several sharp lines appear. The results are discussed in relation to the structural changes at the phase transitions.     

Order-parameter coupling in the improper ferroelectric lawsonite

Low-temperature specific heat and thermal expansion measurements are used to study the hydrogen-based ferroelectric lawsonite over the temperature range 1.8 K ≤ T ≤ 300 K. The second-order phase transition near 125 K is detected in the experiments, and the low-temperature phase is determined to be improper ferroelectric and co-elastic. In the ferroelectric phase T ≤ 125 K, the spontaneous polarization P(s) is proportional to (1) the volume strain e(s), and (2) the excess entropy ΔS(e). These proportionalities confirm the improper character of the ferroelectric phase transition. We develop a structural model that allows the off-centering of hydrogen positions to generate the spontaneous polarization. In the low-temperature limit we detect a Schottky anomaly (two-level system) with an energy gap of Δ ～ 0.5 meV.     

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.