MOLECULAR AND COLLECTIVE PROCESSES IN THE ANTIFERROELECTRIC PHASE OF A CHLORINATED COMPOUND

Abstract

New liquid crystalline substance, (S) 4-(1-methylheptyloxycarbonyl)-3-chlorophenyl 4′-(4-butanoiloxybut-1-oxy)biphenyl-4-carboxylate, exhibiting ferroelectric and antiferroelectric phases have been studied by means of frequency domain dielectric spectroscopy. DSC calorimetric and electrooptic measurements were done to study its phase transitions and electrooptic behaviour. In the antiferroelectric SmC_A* phase one of the dielectric relaxation modes exhibits a non-Arrhenius behaviour. The plots of critical frequencies and dielectric increments vs. temperature show an anomalous behaviour of the relaxation processes in the neighbourhood of the ferroelectric — antiferroelectric phase transition. Reversal current method reveals one current peak in the ferroelectric phase and two in the antiferroelectric one. Temperature dependencies of tilt angle, spontaneous polarization, switching time and transmittance are also presented and discussed in scope of the mean-field theory.     

Comparison of analysis of dielectric spectra of PCL in the ε1 and the M1 formalism

The complex dielectric modulus, M¹(ω, T), for poly(ε-caprolactone) has been obtained by inverting the complex dielectric permittivity data, ε¹(ω, T) recorded in a wide temperature and frequency range. The analysis of the dielectric loss modulus spectra M″(ω, T) have been performed by using a simulated annealing Monte Carlo procedure in order to extract the relaxation parameters for each relaxation mode. Besides the local modes γ and β, the segmental α mode associated to the glass transition, the conductivity and the interfacial polarization peaks could be analyzed with a better precision than by using the conventional non-linear least squares method in ε″ domain. The merging of the α and β modes at high temperatures is much better defined due to the less significant contribution of the ionic conductivity in M¹ formalism.     

Structural, thermal and electrical properties of PVA-LiCF3SO3 polymer electrolyte

The development of polymeric systems with high ionic conductivity is one of the main objectives in Li rechargeable battery. In the present study, the different composition of PVA-LiCF₃SO₃ polymer electrolyte has been prepared by solution cast technique using DMSO as solvent. The FTIR study confirms the polymer-salt complex formation. The amorphous nature of the polymer has been confirmed by XRD analysis. DSC measurements show decrease in T_g with increasing salt concentration. The temperature dependent conductivity obeys Arrhenius relationship. The maximum conductivity has been observed in the order of 7 × 10^− 4 S cm^− 1 for 25 mol% of LiCF₃SO₃. The activation energy has been found to be 0.16 eV. The two peaks have been observed in the dielectric loss spectrum which shows two types of relaxation α and β.     

Study of CaO-WO3-P2O5 glass system by dielectric properties, IR spectra and differential thermal analysis

Dielectric constant ε^′, loss tanδ and ac conductivity σ_ac of 40CaO-xWO₃-(60−x)P₂O₅ (with 0?x?15) glasses are studied over a range of frequencies and temperature. The dielectric breakdown strength of these glasses is also determined at room temperature. The values of dielectric parameters, viz., ε^′, tanδ and σ_ac of CaO-P₂O₅ glasses are found to decrease with the introduction of WO₃ up to 3 mol% and increase with further increase in the concentration of WO₃; the probable reasons for such an increase are identified and explained with the aid of IR spectra and differential thermal analysis of these glasses. The variation of tanδ with temperature at different frequencies of CaO-P₂O₅ glasses has exhibited dielectric relaxation effects with decreasing relaxation intensity with increase in the concentration of WO₃ from 0 to 3 mol%; such relaxation effects seem to have been absent in glasses containing WO₃ beyond 3 mol%. The relaxation phenomenon has been analysed by a pseudo-Cole-Cole plot method and the possible mechanism responsible for such relaxation effects has been suggested.     

On the mechanism of dielectric relaxation in vanadium phosphate glasses

The mechanism of dielectric relaxation in xV₂O₅?(100?x)P₂O₅ glasses (x=50?70) has been investigated using the stimulated dielectric relaxation currents (SDRC) technique. The dielectric relaxation in metal-glass-metal systems is found to be non-linear with regard to voltage bias. Schottky barrier formation at the metal-glass interface, rather than a conventional Debye-type relaxation, is suggested to account for the observed behavior. The density of states N(E_F) as determined from the SDRC is in excellent agreement with the density of paramagnetic states found by the EPR technique.     

On the role of the β process as precursor of the α relaxation in aromatic polyesters

By performing broad band dielectric spectroscopy measurements in a series of amorphous aromatic polyesters we show that different fast modes, contributing to the β relaxation, appear at temperatures below the glass transition temperature, T_g. At high temperatures, (T > T_g) the different β modes tend to merge and the data have to be described by a single β peak. We tentatively assign a molecular origin to each of the different β modes. But also we find a strong connection among the merged β processes and the precursor of the structural α relaxation, implying that this relaxation may posses an important degree of intra-segmental cooperativity.     

Investigation on dielectric relaxations of PVP-NH4SCN polymer electrolyte

Poly (N-vinyl pyrrolidone) (PVP) and ammonium thiocyanate (NH₄SCN) based polymer films with different compositions have been prepared by solution casting technique. The amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The FTIR analysis confirms the complex formation of the polymer with the salt. The conductivity analysis shows that the 20 mol% ammonium thiocyanate doped polymer electrolyte has high ionic conductivity and it has been found to be 1.7 × 10⁻⁴ S cm⁻¹, at room temperature. From the admittance plot, the activation energy has been found to be low for 20 mol% salt doped polymer electrolyte. The dielectric behavior has been analyzed using dielectric permittivity (ε^∗), dissipation factor (tan δ) and electric modulus (M^∗) of the samples.     

Thermal and EPR investigations of thallium gallium disulphide single crystal

In this research, the results of the differential scanning calorimetry (DSC) and electron paramagnetic resonance (EPR) investigations of TlGaS₂ single crystal are presented. Specific heat capacity (C_p) anomalies of layered TlGaS₂ have been obtained by using a new DSC technique for such crystals. Remarkable heat capacity anomalies have been revealed at the temperatures of 137.7 K, 174.5 K and 238.5 K. It is found that the anomalies appear at maximum with a small deviation (by 3‐4%) from the regular values, and C_p discontinuity amounted to approximately 5%. Additionally, EPR spectra of Fe doped TlGaS₂ single crystals have been recorded at various temperatures down to 6 K for different orientations of the applied magnetic field. Transformations of present EPR spectra are not sufficient for the confirmation of structural phase transitions, in contrast to the cases in iso structural TlInS₂ and TlGaSe₂ compounds. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Flux growth and low temperature dielectric relaxation in piezoelectric Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 single crystals

Single crystals of Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT 91/9) have been grown by flux method after modifications in temperature profile, flux ratio and addition of excess ZnO/B₂O₃ which resulted in enhanced perovskite yield (more than 95%). Only a few crystals showed the presence of pyrochlore phase/variation in composition. A comparative characterization of these crystals were carried out in respect of piezoelectric charge coefficient d₃₃, dielectric constant, ac conductivity and hysteresis loop after cutting and poling the crystals along [001] direction. The total activation energy for conduction has been found to increase with Ti‐content in the sample. The effect of ZnO on growth behavior has been analyzed. A detailed analysis of PZNT (91:9) has been carried out at low temperature in respect of the various thermodynamic parameters related to the dielectric relaxation mechanism, like optical dielectric constant, static dielectric constant, free energy of activation for dipole relaxation, enthalpy of activation and relaxation time, have been calculated in the vicinity of transition temperature in the lower temperature region. The activation energy for relaxation at ‐10 and ‐49 °C have been found to be 0.09 and 0.02 eV respectively. The results were analyzed and a detailed dielectric analysis and low temperature relaxation behavior of PZNT crystals were interpreted. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman Spectroscopy Studies of Reorientations in Isotropic Phase of Alkoxyazoxybenzenes

Abstract

Raman spectra for isotropic phase of PAA, PAP and HOAB were recorded. Three benzene rings vibrations were chosen for quantitative analysis and the choice is discussed for different PAA deuteration. The separation of vibrational and rotational relaxation was performed. Vibrational relaxation is a dominating process, but ca. 10% of total bandshape can be attributed to rotational relaxation. Rotational correlation times τ2 were calculated for all studied substances to be of the order 10^?11 s. τ2 is connected with the rotation around the long molecular axis and supports the correlation time τ₁ received from the dielectric relaxation measurements.     

Glass transition and segmental dynamics in poly(dimethylsiloxane)/silica nanocomposites studied by various techniques

We report new results on segmental dynamics and glass transition in a series of poly(dimethylsiloxane) networks filled with silica nanoparticles prepared by sol-gel techniques, obtained by differential scanning calorimetry (DSC), thermally stimulated depolarization currents (TSDC), broadband dielectric relaxation spectroscopy (DRS) and dynamic mechanical analysis (DMA). The nanocomposites are characterized by a fine dispersion of 10 nm silica particles and hydrogen bonding polymer/filler interactions. The first three techniques indicate, in agreement with each other, that a fraction of polymer in an interfacial layer around the silica particles with a thickness of 2–3 nm shows modified dynamics. The DSC data, in particular measurements of heat capacity jump at T_g, are analyzed in terms of immobilized polymer in the interfacial layer. The dielectric TSDC and DRS data are analyzed in terms of slower dynamics in the interfacial layer as compared to bulk dynamics. We employ a special version of TSDC, the so-called thermal sampling (TS) technique, and provide experimental evidence for a continuous distribution of glass transition temperatures (T_g) and molecular mobility of the polymer in the interfacial layer, which is consistent with the DRS data. Finally, DMA results show a moderate slowing down of segmental dynamics of the whole polymer matrix (increase of glass transition temperature by about 10 K as compared to the pure matrix).     

Dielectric relaxation study of chalcogenide glasses

The paper reports dielectric measurements carried out for a variety of threshold and memory alloys of glassy AsGeTe and SeGeTe at different temperatures (83 to 373 K) and various frequencies (0.2, 0.5, 1.0, 2.6 and 5.0 MHz). It is found that the glassy system of chalcogenides exists in the form of molecular dipoles which remain frozen at low temperatures and, as the temperature is increased, the molecules attain freedom of rotation at temperatures which are sometimes as low as 253 K. All the materials displayed dielectric dispersion in the radio frequency range. Gevers' formula has been used to calculate the dielectric loss (?′') and loss-angle (tan δ) from the measured values of the real part of dielectric constant (?′). The curves: log ?′ versus temperature, ?′ versus log ω, ?″ versus log ω, tan δ versus log ω and tan δ versus temperature, gave a direct evidence of the existence of a Debye-type relaxation having a wide distribution of relaxation times.Cole-Cole diagrams have been used to determine the distribution parameter (α) and the molecular relaxation time (τ). The temperature dependence of α and τ for all the alloys is consistent with the “molecular relaxation mechanism”. The paper also reports accurate values of the static and optical dielectric constants for all the alloys.Eyring's relaxation rate equations have been used to determine the free energy of activation (ΔF), and enthalpy of activation (ΔH) for all the alloys. These results indicate the existence of a stronger intermolecular interaction for SeGeTe alloys. mott's concept of “dangling bonds” has also been used to explain the existence of a stronger intermolecular interaction, and hence a greater density of defect states in case of SeGeTe as compared with AsGeTe alloys.It has been finally concluded that the dielectric behaviour of chalcogenide glasses, in general, can be successfully explained by using the theory of molecular relaxation.     

Dielectric characteristics of Ce3+ doped Sr0.61Ba0.39Nb2O6 with Cole‐Cole plots technique

In this paper, we have investigated two‐relaxator mechanism and dielectric characteristics of Ce³⁺ doped Sr_0.61Ba_0.39Nb₂O₆ with dielectric spectroscopy measurements. The crystal undergoes a ferroelectric phase transition at 340 K. The temperature dependence of the real and imaginer part of the complex dielectric susceptibility in vicinity of ferroelectric‐paraelectric phase transition has been studied in the frequency region 0.1 kHz–10 MHz. The measurements of the dielectric constant of the real and imaginer parts show strongly frequency dependence. The investigations of the dielectric constant revealed a non‐Debye type dielectric relaxation for Ce⁺³ doped SBN61 by using Cole‐Cole plots. It reveals the coexistence of the two dielectric relaxators in vicinity of the phase transition. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,characterization, and mesomorphic investigation of vinyl ester-substituted chalcones and effect of lateral ‒NO2 and ‒OCH3 group

A novel homologous series of α-4-(4′-n-alkoxy cinnamoyloxy) phenyl β-2″-nitro, 3″–4″ di methoxy benzoyl ethylenes, H_2n+1CnO?C₆H₄?CH?CH?COO?C₆H₄?CO?CH?CH?C₆H₂(NO₂) (OCH₃)₂ (n = 1–8, 10, 12, 14, 16, 18) has been synthesized. All these compounds have been characterized by suitable spectroscopic techniques. C₁ homologue is nonmesogenic, while C₂ homologue shows enantiotropic nematogenic property and the rest of the homologous (C₃?C₁₈) displayed enantiotropically smectogenic plus nematogenic phase. Phase transition temperatures and textures of the LC phase were determined by an optical polarizing microscopy (POM) equipped with a heating stage. The mesomorphic properties of these compounds were confirmed by differential scanning calorimetry (DSC) analysis.     

Liquid Crystals: A Bibliography for 1975

Abstract

The static dielectric constants of biphenyl-4-p-n-alkoxybenzoates have been measured as functions of temperature. The dielectric anisotropy (δ?) for the successive homologues (hexyl to undecyl) shows an alternation similar to that exhibited by the nematic-isotropic transition temperature (T _NI). The dispersion of ?_∥ in the frequency range of 0.1-15 MHz has been studied for four successive members of biphenyl-4-p-n-alkoxybenzoates (heptyl to decyl derivatives) as well as of trans-p-n-alkoxy-α-methyl-p'-cyanophenyl cinnamates (eighth to eleventh members). For both series the relaxation frequency (f _R) and the frequency of dielectric isotropy (f _o) evaluated at a common relative temperature show an alternation similar to T _NI. For any given compound the Arrhenius plots for f _R and f _o give the same value of the activation energy (W). In the case of the biphenyl esters the vaue of W is the same for the seventh and eighth members, but increases for the higher members which exhibit a smectic phase at lower temperatures. On the contrary for cinnamic acid esters W is found to be the same for all homologues irrespective of whether the nematic phase is preceded by a smectic phase or not.     

Crystallization and optical properties of CaWO4 and SrWO4

Single crystals of calcium tungstate and strontium tungstate have been grown by double decomposition flux reaction technique using lithium chloride as flux. Growth conditions are optimized to synthesize well faceted crystals. Effect of primary and secondary flux density in the growth charge has been studied. Thermogravimetric study reveals that the grown crystals are highly stable in the temperature range 25 – 1000°C. Analysis of optical absorption normal to the ab‐plane in the spectral range of 200 – 800 nm reveals the true absorption edge, the nature of transition being the allowed indirect one at 4.60 eV and 4.56 eV respectively for CaWO₄ and SrWO₄. The crystals have been characterized by determining useful pertinent optical and dielectric parameters. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Dielectric and Optical Properties of the Homologous Series of Cyano-Alkyl-Biphenyl Liquid Crystals

The electric permittivities, refractive indices and densities of the homologous series of alkyl-cyano-biphenyls (C_nH_2n+1.φ.φ.CN) have been measured as a function of temperature in the nematic phases for n = 5 to 9, and in the smectic phases for n = 8 and 9. The results have been analysed in terms of the Maier and Meier theory to yield values for the molecular dipole moments and polarizabilities. Kerr effect measurements on dilute solutions of 44′-n-pentyl-cyano-biphenyl at different temperatures are reported, and in conjunction with similar dielectric and optical measurements have provided results for the free molecule dipole moment and polarizabilites; values for the higher homologues are predicted using a bond additivity model. Bordewijk's theory is applied to the permittivity measurements, and using appropriate molecular parameters, dipole-dipole correlation factors are calculated.     

Effect of doping method on the formation of charge-compensating defects in PbMoO4:Nd3+ crystals

PbMoO₄:Nd³⁺ single crystals have been grown using different doping schemes. Their dielectric properties have been studied in the temperature range of 20?C550°C at frequencies from 25 to 10⁶ Hz. The activation energies of dielectric relaxation are determined for all samples, and the Nd³⁺ luminescence decay kinetics is studied. The most realistic models of activator centers in PbMoO₄:Nd³⁺ crystals are proposed based on the optical and dielectric spectroscopy data.     

Thermal characterization of a vinylidene fluoride-trifluorethylene (75–25) (%mol) copolymer film

Vinylidene fluoride-trifluorethylene (VDF-TrFe) copolymers – exhibits ferroelectric properties due to the special arrangement of the chain units in the crystalline phase. The co-polymers have attracted intense scientific and technological interest due to the possibility of studying the ferroelectric phase transition, as it occurs before the melting of the material. Being that the piezo- and pyroelectric properties of the material are the most interesting from a practical point of view, they have been intensively studied in the recent years. Nonetheless, there is a lack of information about the thermal behavior of other relevant characteristics of the samples. In this work, P(VDF-TrFE) (75/25) has been characterized by mechanical tests and a series of thermal analysis techniques, including thermal mechanical analysis (TMA) and differential scanning calorimetry (DSC). The films exhibit slight mechanical anisotropy, and in the longitudinal direction larger mechanical properties, due to the higher structural organization. DSC results show two well-defined peaks corresponding to the ferroelectric-paraelectric transition and the melting of the paraelectric phase at higher temperatures. Two relaxation processes were found (β and α_c) by dynamic mechanical analysis (DMA). The β process, attributed to segmental motions in the amorphous phase, appears at the same temperature in both directions, but its intensity was found to be higher for the films tested in the longitudinal direction. At higher temperature, the α_c relaxation was related to the thermal variation of the dimensions of the films in the longitudinal direction during heating, recorded by TMA.     

Dielectric relaxation and morphologic properties of CaCu3Ti4O12 doped with GeO2

CaCu₃Ti₄O₁₂ (CCTO) is a material with giant dielectric constant, presenting good stability over a wide temperature and frequency ranges. The preparation method and doping has a great influence on the microstructure and dielectric properties of this material. In this work, doping CCTO with 2–10 wt% GeO₂ has been shown to increase the dielectric constant. We studied the prepared samples by X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance spectroscopy. X-ray diffraction shows the presence of nanocristals. Grains and grain boundaries compositions have been observed by scanning electron microscopy with energy dispersive X-ray spectrometry mapping. Impedance spectroscopy measurements, in the frequency range from 75 kHz to 30 MHz, and temperature from 250 to 325 K, have been performed. The data were analyzed using the Cole–Cole model of dielectric relaxation.