Antiferroelectric and ferroelectric phase transitions of the displacive and order-disorder type in PbZrO3 and PbZr1-xTi x O3 single crystals

For PbZrO₃ and PbZr_0.99Ti_0.01O₃ single crystals the first order Raman light scattering spectra in the paraelectric phase have been analysed. In lead zirconate two kinds of crystals, with and without a transient phase, were investigated. It was found that temperature dependence of the defect-induced soft mode frequency in the paraelectric phase has a negligible contribution to the low-frequency dielectric response. From the point of view of strong dielectric relaxation in the range of 10⁶–10⁹ Hz, which originates in a disorder of the lead sites, crossover of the order-disorder and displacive type of antiferroelectric phase transition in lead zirconate is considered: the phase transition mechanism is neither purely displacive nor order-disorder. Contribution of physical phenomena responsible for the ε(ω,T) dielectric response at low frequencies of an external electric field are described.     

Parameters of LC molecules’ movement measured by dielectric spectroscopy in wide temperature range

Dielectric properties of a nematic liquid crystal (NLC) mixture ZhK-1282 were investigated in the frequency range of 10²–10⁶Hz and a temperature range of ?20 to 80?°С. On the basis of the Debye’s relaxation polarization model dielectric spectra of temperature dependence of the orientational relaxation time τ and the dielectric strength δe were numerically approximated at the parallel orientation of a molecular director relative to alternating electric field. Influence of ester components in the mixture plays crucial role in relaxation processes at low temperature and external field frequency. The activation energy of the relaxation process of a rotation of molecules around their short axis was measured in a temperature interval of ?20 to ?+15?°С in which the dispersion of a longitudinal component of the dielectric constant takes place. The energy of potential barrier for polar molecules rotation in the mesophase was calculated. The value of the transition entropy from the nematic to isotropic phase was obtained from this calculation. The values of the coefficient of molecular friction and rotational diffusion were obtained by different methods. The experimental data obtained are in a satisfactory agreement with the existing theoretical models.     

Dielectric investigations in the nematic and hexatic smectic B phases of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl

Temperature-dependent dielectric characterization of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl (HIEB), which exhibits smectic B and nematic phases, has been carried out over the frequency range of 1 Hz to 10 MHz for homeotropic and planar alignment of sample molecules. This compound shows positive dielectric anisotropy (Δε = ε _∥ ? ε _⊥ > 0) in the nematic (N) phase. One mode of dielectric relaxation showing Arrhenius behaviour has been detected in the hexatic smectic B (SmB) phase. Various electrical parameters, namely, dielectric anisotropy, relaxation frequency and activation energy, have been determined in the N and SmB phases.     

Investigation of the effect of gamma rays on electrical properties of chlorinated poly (vinyl chloride)

Dielectric constant, dielectric loss and AC conductivity were measured, in the frequency range 100 Hz to 5 MHz in chlorinated poly (vinyl chloride) (CPVC) before and after exposure to gamma irradiation at doses between 5.0 KGy and 50.0 KGy. The frequency dependencies of ε′, ε″ and σ_AC at 30 °C were investigated. A relaxation peak in the dielectric loss and a corresponding step in the dielectric constant have been observed, in the frequency ranges 10³ Hz to 10⁴ Hz. The dielectric constant ε′, dielectric loss ε″ and AC conductivity σ_AC are also found to increase at heating up to 100 °C. In addition the effect of gamma irradiation on the frequency dependencies of ε′, ε″ and σ_AC was measured at room temperature. The gamma irradiation leads to an increase in the efficiency of soft segments. Furthermore, the DC electrical conductivity of both the irradiated and non-irradiated samples was investigated. The induced electrical conductivity and the activation energy were measured, at various temperatures, as a function of gamma dose. It was found that the gamma radiation has a definite effect on the DC conductivity of the CPVC polymer.     

Optical spectra of triglycine sulfate crystals in the range of 7–33 eV and its changes at phase transition

Pseudo-dielectric functions ?ε₁(E)? and ?ε₂(E)? of triglycine sulfate (TGS) crystal have been obtained in the range of 7–33 eV for different temperatures close to ferroelectric phase transition by spectral ellipsometry using the synchrotron radiation source BESSY II. These dielectric functions ε₁(E) and ε₂(E) have also been calculated from first principles using CASTEP CAmbridge Serial Total Energy Package code together with the band structure and density of electronic states of the crystal. Experimental and theoretical dielectric functions agree satisfactorily. A characteristic decrease of temperature dependences of the dielectric losses tgδ(T) and related values just below the phase transition temperature T _c have been found and discussed.     

Structure and dielectric properties of PZT-type ceramics with the diffuse phase transition

In the present work the (Pb_0.84Ba_0.16)(Zr_0.54Ti_0.46)O₃ (PBZT) solid solution has been synthesized. The process of preparation was investigated by simultaneous thermal analysis (STA) and X-ray diffraction method. The hot pressing method was utilized for densification of ceramic samples. Dielectric properties of donor- and acceptor-doped PZT-type ceramics were measured within the temperature range including the phase transition region. Frequency-dependent relaxation behaviour in PBZT ceramics was found. The structural phase transition at T?=?(517?±?3)?K was determined by X-ray diffraction method. Arrhenius plot of total conductivity derived from ac impedance spectroscopy measurements was used for characterisation of phase transition. Changes in activation energy were found characteristic of phase transition in PBZT ceramics.     

Lattice mediated interactions and ferroelectric anomalies in the crystal (CH3NH3)5Bi2Cl11 (PMACB)

Abstract

A two-sublattice compressible pseudospin model has been constructed to describe the behaviour of the spontaneous polarisation of PMACB in the temperature region comprising the ferroelectric phase transition (T=307K) and the isomorphous anomaly (T= 180 K). A strong coupling of pseudospins with a “pancake” strain ?(2ε₃₃ ? ε₁₁ - ε₂₂) /3 resulting from the comparison of the model with the experimental spontaneous polarisation agrees with the existing data on the dielectric susceptibility, and on the specific heat. The ferroelectric phase transition then turns out to be close to a tricritical point. The numerical values of the parameters of the model show how the ferroelastic phase transition (T=260K) can occur in this crystal without any discernible effect on the specific heat and on the dielectric susceptibility.     

Coexistence of glass and ferroelectric order in deuterated betaine phosphate0.05 betaine phosphite0.95 crystals

The dielectric spectra of ferroelectric hydrogen bonded betaine phosphate_0.05 betaine phosphite_0.95 (DBP_0.05DBPI_0.95) was investigated in the very wide temperature (300–20 K) and frequency (20–35 GHz) regions. The dielectric dispersion was analyzed in terms of distribution of relaxation times, using Tichonov regularization method. Strongly asymmetric and broad distribution of relaxation times below ferroelectric phase transition temperature T _c?≈?253 K clearly differs from the one that is usually observed in ferroelectrics. The observed disorder in deuterons system close to ferroelectric phase transition temperature is an embryo of coexistence ferroelectric order and dipolar glass disorder observed at low temperatures.     

Dielectric spectroscopy of a high-polarization ferroelectric liquid crystal

Dielectric spectroscopy investigations in the frequency range 50?Hz to 1?MHz have been carried out on a new ferroelectric liquid-crystalline material (S-(-)-4-(2-n-hexylpropionyloxy)biphenyl-4′-(3-methyl-4-decyloxy)benzoate) possessing a relatively large spontaneous polarization (P _s?～?240?nC?cm^?2) and containing a lateral methyl group on the aromatic ring of the alkoxybenzoate unit. The effect of temperature on the dielectric relaxation modes has been investigated in the SmC* and N* phases. From dielectric dispersion data, relaxation frequency and dielectric strength of all detected relaxation modes have been evaluated and discussed. A new surface-like mode of relaxation frequency ～11?kHz and dielectric strength 3.8, is seen to appear in the SmC* phase.     

Study of dielectric anisotropy and other related parametersof a liquid crystal compound 7OAOB

Temperature-dependent dielectric anisotropy has been measured for the compound 4,4′-di-n-heptyloxy-azoxy benzene (7OAOB) by using a digital LCR bridge (HIOKI 3532-50 LCR HiTESTER). The compound 7OAOB is found to exhibit negative dielectric anisotropy in the nematic and smectic-C phase. Frequency-dependent electrical conductivity has been measured for this compound. The dc conductivity has also been obtained from frequency-dependent total conductivity studies by using universal power law equation. The activation energy of the dc conduction process and relaxation time has been determined in different mesophases. The behavior of splay elastic constant (K₁₁) with temperature has been examined for this compound. From the studies of UV-visible spectra, the values of energy band gap have been evaluated.     

Effect of high electric fields on the nematic to isotropic transition in a material exhibiting large negative dielectric anisotropy

We report the experimental high electric field phase diagram of a nematic liquid crystal which exhibits a large negative dielectric anisotropy. We measure simultaneously the birefringence (Δn) and the dielectric constant (epsilon_⊥) at various applied fields as functions of the local temperature of an aligned sample. We also measure the higher harmonics of the electrical response of the medium. The following experimental results are noted: (i) enhancement of orientational order parameter S in the nematic phase due to both the Kerr effect and quenching of director fluctuations; (ii) enhancement in the paranematic to nematic transition temperature (T_PN) with field; (iii) divergence of the order parameter susceptibility beyond the tricritical point as measured by third harmonic electrical signal; (iv) a small second harmonic electrical signal which also diverges near T_PN, indicating the presence of polarised domains. Our measurements show that ΔT_PN(= T_PN(E)-T_NI(0)) varies linearly with |E| whereas the Landau de Gennes theory predicts a dependence on E². It is argued that the quenching of director fluctuations by the field makes the dominant contribution to all the observations, including the thermodynamics of the transition.     

Dielectric permittivity studies of nematogenic compounds and their binary mixtures showing induced smectic Ad phase

The binary mixture of 4-n-pentyl phenyl 4-n′-hexyloxy benzoate (ME6O.5) and p-cyanophenyl trans-4-pentyl cyclohexane carboxylate (CPPCC) shows the presence of induced Smectic A_d phase. In the present work the phase diagram as well as static dielectric permittivity measurements of different mixtures throughout the composition range, are reported. The observed variation of dielectric anisotropy with molar concentration in the nematic and smectic phases is explained, assuming the formation of both homo- and hetero-dimers in the mixture.     

Diffuse phase transition of BaTi0.6Zr0.4O3 relaxor ferroelectric ceramics

BaTi_0.6Zr_0.4O₃ ceramic was prepared through solid state reaction route. X-ray diffraction showed that the composition has cubic perovskite structure with space group Pm-3m at room temperature. Temperature dependency dielectric study of the ceramic has been investigated. Bulk density was determined using Archimedes principle and found to be ～97% of X-ray density. The average grain size in the pallet is measured by an optical microscope and found to be 22.23?µm. The dielectric measurement revealed diffuse phase transition of second-order, where dielectric peak temperature (T _m) is dependent of frequency showing relaxor-type behaviour. A clear deviation from Curie–Weiss law is observed in the paraelectric region. The dielectric relaxation rate follows the Vogel–Fulcher relation with E _a?=?0.1020?eV, T _f?=?106?K, ν₀?=?8.5?×?10¹¹?Hz.     

Dielectric losses in the triglycine sulfate crystal under heating and cooling

Temperature dynamics of the dielectric spectra and domain structure in the triglycine sulfate (TGS) hydrogen-containing ferroelectric under heating and cooling has been studied using the dielectric spectroscopy and atomic-force microscopy methods. The dielectric spectra are analyzed by the temperature-frequency dependences of the losses ε″ and by the temperature behavior of the maximum losses ε″_max in the dispersion region at frequencies ranging from 102 to 106 Hz. A dynamic conductivity model is proposed for calculating temperature dependences of losses ε″_max. The domain structure dynamics during the heating and cooling of the TGS crystal near the phase transition is studied using the in situ piezoresponse force microscopy. It is experimentally and theoretically shown that the relaxation dispersion is governed by the binding of strongly correlated dipoles with the main lattice that serves as a thermostat.     

Dielectric and calorimetric studies on 1BC1EPOPB feroelectric liquid crystal having a large spontaneous polarization

Experimental investigations on the ferroelectric liquid crystal, R-4′(1-butoxycarbonyl-1-ethoxy) phenyl 4-(4-octyloxy phenyl) benzoate (1BC1EPOPB) of large spontaneous polarization (P _S(+) = 240?nC?cm^?2), using dielectric and calorimetric techniques, are reported. The temperature range of 25.0–125.0°C has been chosen for dielectric measurements. Dielectric dispersion studies are carried out in the temperature range 45.0–75.0°C and in the frequency range 2?Hz to 2?MHz for the smectic A, smectic C* and smectic X phases. A new phase called ‘smectic X’ has been found around 56.3°C. The transition temperatures identified by the dielectric dispersion studies for different phases and those given by DSC techniques are in close agreement.     

Properties of (Bi1/9Na2/3)(Mn1/3Nb2/3)O3 analysed within dielectric permittivity,conductivity, electric modulus and derivative techniques approach

The (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ ceramics with perovskite structure were sintered. The XRD test proved that the samples are cubic (a?=?3.920?±?0.001?Å). Microstructure and atomic composition were determined with a SEM (JSM-5410) equipped with energy dispersion X-ray analyser (ISIS-300). The fluctuation in the chemical composition was found indicating on local disorder. Broadband dielectric spectroscopy in the range 10^?1–3?·?10⁷?Hz was applied within the range of 100–650?K. The real, ?′(f,?T), and imaginary, ?″(f,?T), parts of complex dielectric permitivity characteristics, both in the temperature and frequency domain, show relaxation processes partially covered by electric conductivity. At high temperatures the electric conductivity exhibits a thermally activated behaviour σ(f,?T)?∝?exp(?E _a/kT) but the variable range hopping (VRH) dependence σ?∝?exp[?(T ₀/T)^1/4] is manifested at low temperatures. The derivatives technique in the frequency (??log??/??log?ω) and temperature (??log??/?T) domain enabled various relaxation processes to be distinguished. The data converted to electric modulus representation, M*(f,?T)?=?1/?*, exhibited clearly resolved relaxation peaks. The relaxation times obtained from the peaks position show a slightly non-Arrhenius temperature behaviour with the activation energy varying in 0.4–0.6?eV range and characteristic time of the electric conductivity relaxation of the order of 10^?12?s. The relaxation times can be fitted at better accuracy with the VRH dependence where T ₀ are of the order of 10⁸?K. It is shown that the low frequency ac-conductivity converges to dc-conductivity and the relation σ(0)?～?ω_m?～?τ_m ^?1 typical for the disordered solids applies. The conduction current relaxation relationship behaves in accord with the VRH system: σ_dc?∝?(T/T ₀)^q (e ²/kT) ω_c, where ω_c?=?ν_ph exp[?(T ₀/T)^1/4] is valid for the locally disordered (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ compound.     

Polar relaxation mode in PbZrO3 crystals

Abstract

In antiferroelectric lead zirconate crystal with one phase transition a nearly monodispersive dipolar relaxation has been found in the paraelectric phase and temperature range 20 K below T _c in the frequency region 20—3 ′ 10⁵ Hz. This relaxation has a dominating influence on the temperature dependence of dielectric susceptibility. Relaxation time obeys the Arrhenius law increasing up to 1.5 ′ 10^?2s (11 Hz) at T _c and then exhibiting a distinct jump.     

Influence of sintering conditions and doping on the dielectric relaxation originating from the surface layer effects in CaCu3Ti4O12 ceramics

Detailed investigations into the dielectric dispersion phenomenon in the giant dielectric constant material CaCu₃Ti₄O₁₂ (CCTO) around room temperature revealed the existence of two successive dielectric relaxations. In the temperature domain, a new dielectric relaxation was clearly observed around 250 K, in addition to the well-investigated dielectric relaxation close to 100 K. The effect of sintering and doping (La³⁺) on the strength of these dielectric relaxations were studied in detail. The sintering temperature as well as its duration was found to have tremendous influence on the dielectric relaxation that was encountered around 250 K. This Maxwell-Wagner (M-W) type of relaxation was found to be originating from the surface layer containing the Cu-rich phase, which was ascribed to the difference in the oxygen content between the surface and the interior of the sample. Interestingly, this particular additional relaxation was not observed in La_2/3Cu₃Ti₄O₁₂, a low dielectric constant member of the CCTO family, in which the segregation of Cu-rich phase on the surface was absent. Indeed the correlation between the new relaxation and the presence of Cu-rich phase in CCTO ceramics was further corroborated by the absence of the same after removing the top and bottom layers.     

Dielectric investigation on some binary mixtures of hockey-stick-shaped liquid crystal and octyloxy-cyanobiphenyl

We report the measurement of temperature-dependent dielectric parameters in some binary liquid crystal mixtures comprising of a hockey-stick-shaped mesogen 4-(3-decyloxyphenyliminomethyl) phenyl-4-decyloxycinnamate (SF7) and calamitic compound 4′-octyloxy-4-cyanobiphenyl (8OCB). All the investigated mixtures possess a large positive dielectric anisotropy (Δε), although a noticeable reduction has been found by increasing the diverse-shaped dopant concentration. Investigation on the pretransitional behavior in the vicinity of isotropic to nematic (I–N) phase transition suggesting a tricritical character for all the studied mixtures. Parameterization of dielectric permittivity close to the nematic to smectic-A (N–Sm-A) phase transition exhibits non-universal values of the critical exponents describing a second-order nature of the transition. Systematic variation of critical exponents against dopant concentration and McMillan ratio reveals a well consistency with those obtained from the high-resolution optical birefringence measurements.     

Phase transitions in CuBiP2Se6 crystals

Investigation results of dielectric (20?Hz–1?MHz) properties of layered CuBiP₂Se₆ crystals are presented. The temperature dependence of the static dielectric permittivity reveals the first-order “displacive” antiferroelectric phase transition at T _c?=?136?K. In the paraelectric phase, at low frequencies, dielectric spectra are highly influenced by the high ionic conductivity with the activation energy of 2473?K (0.21?eV). In the antiferroelectric phase the electrical conductivity and its activation energy (531.1?K (0.045?eV)) are considerably smaller. At low temperatures, the temperature behaviour of the distribution of relaxation times reveals complex freezing phenomena. A part of long relaxation time distribution is strongly affected by external direct current (DC) electric field and it is obviously caused by antiferroelectric domain dynamics.