Dielectric properties of ten three-ring LC fluorosubstituted isothiocyanates with different mesogenic cores

Results of the static and dynamic dielectric investigations of 10 liquid crystalline compounds consisting of three rings (phenyl or cyclohexyl) with the n-propyl and isothiocyanato terminals, fluoro lateral substitutes, and different bridging groups (CH₂CH₂ and/or COO) are presented. These compounds form the nematic phase in a broad temperature range. The dielectric parameters are analyzed in relation to the chemical and dipole structures of the molecules. The influence of different structural elements such as rings, bridging groups and fluorosubstitution on the dielectric properties is discussed. The relaxation time and activation enthalpy characterizing the molecular rotations around the short axes were determined. In the nematic phase, the compounds having two fluorine atoms at the lateral positions exhibit a crossover of the principal permittivity components within the megahertz frequency range. This makes them interesting from the application point of view as the so-called dual frequency materials.     

Dielectric and electrooptical properties of hockey-stick-shaped liquid crystal with a negative dielectric anisotropy

We investigated dielectric properties of a hockey-stick-shaped liquid crystal (HLC). Two dielectric relaxation modes were observed at 0.91 kHz and 4.51 MHz. The low frequency relaxation modes in isotropic, smectic, and nematic phases are related to the motion of ions, collective tilt fluctuation, and rotation around the long molecular axis, respectively. Meanwhile, the high frequency relaxation modes in nematic and smectic phases was due to the rotation around the short axis of the molecules and hindered by the resistance of the ITO layers. We also examined the electrooptical response of the 5.0 wt% HLC-doped commercial nematic liquid crystal (LC) mixtures. The birefringence of the LC mixture was slightly increased, while the falling time and the rotational viscosity was decreased in the nematic phase.     

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.     

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.     

The evolution of the molecular relaxation parameters described by the Cole–Cole model at the isotropic-nematic phase transition*

This paper presents the dielectric properties of the isotropic liquid and nematic phase at the phase transition. One strong molecular relaxation is observed in both phases. It is interpreted as related to the relaxation around a short molecular axis, due to the fact that molecules possess a strong longitudinal dipole moment. In the isotropic liquid the relaxation is described by the Debye model, while after entering the nematic phase (at cooling) relaxation becomes described by the Cole–Cole model. The distribution parameter of the Cole–Cole model changes from 0.05 (10 degrees above the temperature of the Iso-N transition) to 0.09 (exactly at the phase transition Iso-N), and finally, it reaches 0.35 (10 degrees below the Iso-N transition). Additionally, we observe that ion contribution to the dielectric response is not influenced by the phase transition. All relaxation parameters are discussed within the context of the phase transition phenomena.     

Comprehensive studies on dielectric properties of p-methoxy benzylidene p-decyl aniline with function of temperature and frequency in planar geometry: A potential nematic liquid crystal for display devices

The dielectric properties of the nematic mesophase, p-methoxy benzylidene p-decyl aniline(MBDA), measured in planar geometry with a function of frequency and temperature are investigated in detail. The complex dielectric permittivity(ε' and ε') is also studied at a bias voltage of 10 V for planar aligned sample cell of nematic mesophase. The dielectric permittivity with bias voltage attains a higher( 2 times) value than that without bias voltage at a temperature of 56℃,which is due to the fact that the linking group of nematic molecules is internally interacted with an applied bias voltage.This is supported by observing an enhanced dielectric permittivity of nematic liquid crystal(LC) in the presence of bias voltage, which can be fully explained as the increasing of the corresponding dipole moment. The dielectric relaxation behaviors of nematic LC are also demonstrated for planar aligned sample cell. The remarkable results are observed that the relaxation frequency shifts into low frequency region with the increase of the bias voltage applied to the planar aligned sample cells. The dielectric relaxation spectra are fitted by Cole–Cole nonlinear curve fitting for nematic mesophase in order to determine the dielectric strength.     

两种不同(Ba,Sr)TiO3薄膜介电-温度特性的研究

研究并比较了两种不同(Ba_0.5,Sr_0.5)TiO₃(BSTO)薄膜介电-温度特性.采用脉冲激光沉积技术在Pt/Ti/SiO₂/Si(100)衬底上制备BSTO薄膜，发现制备条件的不同，可以得到介电性质完全不同的BSTO薄膜.在550℃和氮气氛下制备的BSTO薄膜在常温下具有很高的介电常数，在10kHz下，超过2500，并在200K温度以上介电常数基本不变.它的一些电学性质不同于在正常条件(650℃和氧气氛下)制得的BSTO薄膜，而类似于目前广泛报道的巨介电常数材料如CaCu_３Ti_４O₁₂.两种薄膜介电性质测试结果表明: 氧气氛下制备的BSTO薄膜呈现铁电-顺电相变，符合居里-外斯定律；低温氮气氛下制备的BSTO薄膜，介电弛豫时间和温度的关系符合德拜模型，是热激发弛豫.文中给出了产生这种介电特性的初步解释. 关键词： 薄膜 脉冲激光沉积 介电弛豫     

Pretransitional dielectric properties of nematogenic 4-cyanophenyl-4′-n-heptylbenzoate

This article presents results of the static and dynamic dielectric studies performed for mesogenic 4-cyanophenyl-4′-n-heptylbenzoate in the isotropic (I) and nematic (N) phases. Pretransitional phenomena are observed in the vicinity of I–N phase transition as an anomalous temperature behavior of both the static and the dynamic dielectric properties of the compound. The temperature dependence of the static permittivity is correlated with the entropy change induced by the probing electric field while an anomalous behavior of the dielectric relaxation directly points out for a subdiffusional Brownian rotation of mesogenic molecules in the vicinity of the phase transition.     

Solving the initial condition of the string relaxation equation of the string model for glass transition: part-I

The string model for the glass transition can quantitatively describe the universal α-relaxation in glassformers,including the average relaxation time,the distribution function of the relaxation time,and the relaxation strength as functions of temperature.The string relaxation equation(SRE) of the model,at high enough temperatures,simplifies to the well-known single particle mean-field Debye relaxation equation,and at low enough temperatures to the well-known Rouse-Zimm relaxation equation that describes the relaxation dynamics of linear macromolecules.However,its initial condition,necessary to the further model predictions of glassy dynamics,has not been solved.In this paper,the special initial condition(SIC) of the SRE,i.e.for straight strings and the dielectric spectrum technique that is one of the most common methods to measure the glassy dynamics,was solved exactly.It should be expected that the obtained SIC would benefit the solution of the general initial condition of the SRE of the string model,i.e.for stochastically spatially configurating strings,as will be described in separate publications.     

Dielectric relaxation spectrum of water studied by the site—site generalized Langevin/modified mode-coupling theory

The dielectric relaxation spectrum of water is calculated from the site-site generalized Langevin/modified mode-coupling theory. The main part of the relaxation follows the Debye-type function, and a small deviation from the Debye relaxation is found on the high-frequency side. This tendency is consistent with recent experiments, although the absolute relaxation time does not agree with the experimental value quantitatively. The time development of the longitudinal polarization function resembles the dielectric part of the memory function, and we consider that this is because the dielectric friction dominates the collective reorientation of the dipole moment of water. We performed calculations with different dielectric constants using the reference interaction-site model integral equation, and found that the large gap between the time scales of the dielectric relaxation and the longitudinal polarization relaxation causes the Debye-type dielectric relaxation in our theory when the dielectric friction is dominant in the friction on the collective reorientation of the dipole moment. Namely, the longitudinal polarization relaxation is fast enough to be considered as a white noise to the dielectric relaxation process, so that the relaxation becomes a Markov process. The large gap between the two relaxation times originates from a large local field correction owing to the large dielectric constant of water. It is also suggested that the deviation from the Debye relaxation at the high-frequency side is the manifestation of the slow memory caused by the long-time part of the longitudinal polarization relaxation in the low-wavenumber region.     

Study of dipole dynamics and pre-transitional effects at isotropic to nematic phase transition by low-frequency dielectric relaxation measurements

Thermal microscopy (TM) as well as low-frequency (LF) dielectric relaxation studies are carried out on a nematic liquid crystal (NLC), viz E7 (Merck Ltd, UK). The isotropic to nematic (IN) transition temperatureT _IN determined by TM and LF-dielectric permittivity measurements agrees with the available data. Dielectric loss studies in the frequency region of 5–10?MHz indicate a relaxation (in the kHz region) akin to Debye type off-centered dispersion. The observed nematic relaxation is found to correspond to reorientation (about the short axis) of the nematic dipole to the external field. The temperature variation of the nematic relaxation frequencyf _R is found to follow an Arrhenius shift, with an activation energy of 1.7?eV. Temperature variation of the dielectric strength (Δε = ε _o ? ε_∞) and the distribution parameter α in the nematic phase are discussed. The dynamic response of the nematic dipoles and growth of pre-transitional fluctuations are found to be nonlinear in the vicinity of the IN transition. The value of the exponent α_eff = 0.072 indicates weak growth of transitional fluctuations across the IN transition.     

环氧树脂高温分子链松弛与玻璃化转变特性

环氧树脂是电力设备中广泛应用的一种绝缘材料, 其介电性能受到分子链运动特性的影响. 本文制备了直径为50 mm、厚度为1 mm的环氧树脂试样, 采用差示扫描量热仪和宽频介电谱仪测试了环氧树脂的玻璃化转变温度和介电特性. 实验结果表明, 环氧树脂的玻璃化转变温度为105 ℃, 在玻璃化转变温度以上, 高频段出现了由分子链段运动造成的松弛过程, 低频段出现了由载流子在材料中迁移造成的直流电导过程. 发现环氧树脂不同尺寸分子链段的松弛时间不同, 其松弛时间分布较宽, 计算得到了分子链段在不同温度下的松弛时间分布特性. 分子链松弛峰频率和直流电导随温度的变化关系服从Vogel-Tammann-Fulcher公式. 拟合实验结果得到分子链松弛峰频率和直流电导的Vogel温度和强度系数. 由Vogel温度计算得到了与差示扫描量热测试结果一致的玻璃化转变温度, 约为102 ℃. 结果表明玻璃化转变温度以上环氧树脂的自由体积增大, 分子链段有足够的空间来响应外电场从而产生分子链松弛极化, 载流子有足够的能量在材料中迁移形成电导.     

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.     

Broadband dielectric dispersion in ferroelectric P(VDF-TrFE) copolymer films

Ferroelectric polyvinylidenefluoride-trifluoroethylene copolymer films with different thicknesses are prepared by a solvent-cast technique, by spin coating, and by a horizontal Langmuir–Blodgett technique respectively. The frequency dependent dielectric permittivity of these films is investigated with varying sample thickness and varying temperature in the ferroelectric as well as in the paraelectric phase. A dielectric relaxation according to a Vogel–Tamman–Fulcher law of the relaxation times is found in all samples. However, the relaxation times extracted from the dielectric permittivity in the frequency range are not consistent with the relaxation times determined from the temperature range. An explanation for this behavior is given by a temperature dependent distribution of relaxation times. Additionally, in thin samples a second relaxation with a weak anomalous temperature dependence, i.e. an increasing relaxation time with increasing temperature, is observed at high frequencies. Detailed investigations show that this behavior can be attributed to an electrode effect.     

Diffuse dielectric anomaly of （Na0.5K0.5Bi）0.5TiO3 crystal at high temperature

This paper investigates the dielectric properties of (Na_0.5K_0.5Bi)_0.5TiO₃ crystal at intermediate frequencies (1kHz \le f \le 1MHz) in the temperature range of 30--560℃. A pronounced high-temperature diffuse dielectric anomaly has been observed. This dielectric anomaly is shown to arise from a Debye-like dielectric dispersion that slows down following an Arrhenius law. The activation energy E_r obtained in the fitting process is about 0.69eV. It proposes that the dielectric peak measured at low frequency above 400℃ is not related to the phase transition but to a space-charge relaxation.     

Dielectric properties of LC mixture with induced antiferroelectric phase

Mixture of two liquid crystalline components exhibits the antiferroelectric phase in a broad temperature range at room temperatures, though the two components separately do not show an antiferroelectric phase in a temperature range applied. The dielectric spectroscopy technique combined with measurements of the selective light reflection was used for identification and characterization of the phases and subphases existing in the mixture. In the SmC*_A phase, the low frequency mode characteristic of antiferroelectric phase has been detected. In the broad temperature range between SmC*_A and SmA* phases, no relaxation mode has been detected. The soft mode registered near the phase transition to SmA* phase follows the Curie-Weiss law.     

Magnetic field effects on the electric modulus properties of nematic mixture E7

The molecular dynamics of the homogeneously aligned nematic liquid crystal mixture E7 subject to a magnetic field has been studied. The dielectric spectra study has revealed a low bias magnetic field effect on the evolution of dielectric relaxation spectra occurred at lower (∼kHz) (δ-relaxation) and higher (∼MHz) (α-relaxation) frequency regions. The complex electric modulus, which converted from experimental dielectric spectra, has been analyzed with theoretical model of Debye relaxation. The obtained fitting parameters of relaxation time and strength of dielectric components are shown to vary systematically with the strength of applied magnetic field. A microscopic molecular dynamic model has been proposed to describe the two-step variation of E7 molecular under the bias magnetic field. The results provide implication for magneto-modulation of liquid crystal molecular dynamics under the bias magnetic field.     

Physical meaning of conductivity spectra for ZnO ceramics

With the help of broadband dielectric spectroscopy in a wide temperature and frequency range, the conductivity spectra of ZnO polycrystalline ceramics are measured and the direct-current-like (DC-like) conductivity and relaxation polarization conductivity are observed successively along the frequency axis. According to the classical Debye theory and Cole-Cole equation, the physical meanings of the two conductivities are discussed. It is found that the DC-like conductivity corresponds to electron transportation over the Schottky barrier at the grainboundary. The relaxation polarization conductivity corresponds to electronic trap relaxation of intrinsic point defects (zinc interstitial and oxygen vacancy). When in the high frequency region, the relaxation conductivity obeys the universal law with the index n equal to the index α in the Cole-Cole equation as an indictor of disorder degree.     

CaCu3Ti4O12 陶瓷介电模量响应特性的研究

由于CaCu₃Ti₄O₁₂巨介电常数陶瓷的低频区直流电导较大, 本文采用模量 M"-f频谱表征与分析了低频和高频的两个松弛极化过程. 研究认为, 这两个特征峰属于晶界区Schottky 势垒耗尽层边缘深陷阱的电子松弛过程, 其中高频松弛峰起源于晶粒本征缺陷的电子松弛过程, 而低频松弛峰则为与氧空位有关的松弛极化过程. 对于CaCu₃Ti₄O₁₂这类低频下具有高直流电导的陶瓷材料, 采用模量频谱能更有效地分析研究其损耗极化机理. 关键词： 3Ti₄O₁₂陶瓷')" href="#">CaCu₃Ti₄O₁₂陶瓷 模量 松弛过程 电导     

Dielectric spectroscopy of the SmQ* phase

Liquid crystal possessing two biphenyl moieties in the molecular core and lateral chlorine substitution far from the chiral chain has been studied by dielectric spectroscopy. On cooling from the isotropic phase, the material possesses the frustrated smectic Q* (SmQ*) and SmC_A* phases. It has been confirmed by dielectric spectroscopy that the SmQ* phase can be related to the SmC_A* anti-ferroelectric phase. However, only one relaxation process has been observed in the SmQ* phase, while in the SmC_A*, two relaxations are clearly detectable. It seems that the mode found in the SmQ* can be connected with high-frequency anti-phase mode observed in the SmC_A* phase. Its relaxation frequency is similar to P_H relaxation frequency, but is weaker. The same relaxation has been observed even a few degrees above the SmQ*–Iso phase transition. Another explanation for the mode detected in SmQ* and isotropic phases can be molecular motions around short molecular axis.