Dielectric studies of binary liquid-crystalline mixtures

Six binary liquid-crystalline mixtures have been studied by means of dielectric, microscopic and refractometric measurements. Induced smectic phases appear for four of them. The effective values of the components p_⊥ and p_∥ of the dipole moment per one molecule of the mixtures have been calculated from values of e_∥ and e_⊥. It has been established that the heterocomplexes formed in the mixtures are weak so that they do not cause any changes in the distribution of molecular charges. The observed deviations from linearity of the dielectric constants of the mixtures are caused either by dissociation of the cyanomesogen dimers or by a non-additive behaviour of the mixture density.     

Dynamics of 4,4'-di-n-heptylazoxybenzene (HAB) studied using dielectric and 2H NMR relaxation measurements

Results of studies of 4,4'-di-n-heptylazoxybenzene (HAB) in the isotropic, nematic and smectic A phases are presented. Two experimental methods were employed: broad band dielectric spectroscopy and nuclear magnetic resonance spectroscopy. The complex dielectric permittivity, ε*(ω)=ε'(ω)-iε'(ω), was measured in the frequency range 1 kHz-4 GHz. This allowed two main relaxation processes to be separated in all the phases studied: the low frequency (l. f.) process connected with molecular reorientations around the short axes, and the high frequency (h. f.) process connected with the rotations around the long axes. The corresponding relaxation times and activation enthalpies were obtained. The l. f. relaxation time changes step-wise at the phase transitions, whereas the h. f. relaxation time passes smoothly through all the phases. The measurement of ²H spin-lattice relaxation times was carried out throughout the mesophase range at 61.38 MHz. These data were analysed together with the relaxation times measured at 10.00 and 46.04 MHz, available from previous studies. Using suitable theoretical models the principal components of the diffusional tensor, D_‖ and D_⊥, as well as the diffusion coefficients D_R relative to the internal rotation of the phenyl rings, were determined. The results of both studies are compared and discussed.     

Electrical conductivity and dielectric constant measurements of liquid crystal-gold nanoparticle composites

The behaviour of the anisotropic electrical conductivity of liquid crystal-gold nanoparticle (LC-GNP) composites consisting of a commercially available room temperature nematic compound doped with alkylthiol-capped GNPs has been investigated. The nematic-isotropic transition of the composite decreases nearly linearly with increasing X, the concentration of GNP (in weight %) at a rate of about 1°C /weight %. The inclusion of GNPs increases the electrical conductivity of the system with the value increasing by more than two orders of magnitude for X = 5%. However, the anisotropy in conductivity, defined as the ratio of the conductivity along (σ_∥) and orthogonal (σ_⊥) to the director shows a much smaller but definite decrease as X increases.     

Relationships between oxygen diffusion characteristics of polycrystalline and single crystal 2MgO · TiO2

Self-diffusion coefficients of oxygen in both polycrystalline and single crystal 2MgO·TiO₂ have been measured at an ambient oxygen pressure of about 40 mm Hg over the temperature range 1080–1450°C. A convenient method to estimate the volume diffusion coefficient, D₁, of this polycrystal in which the relative magnitude in D_g (grain boundary diffusion coefficient) with respect to D₁ falls between two extremes, i.e., D_g = D₁ and D_g D₁, is newly proposed, and its plausibility is examined by comparing the resultant D₁ with that of single crystal 2MgO·TiO₂. Not only the magnitude but also the temperature dependence of the “apparent” diffusivity of these polycrystalline particles considerably varied with their particle size. The reason for this semiquantitatively interpreted in terms of the relative magnitude of D_g with respect to D₁.     

NMR study of molecular dynamics in a mixture of two polar liquid crystals (CBOOA and DOBCA)

A mixture containing 70 per cent 4-cyanobenzylidene-4'-n-octylaniline (CBOOA) and 30 per cent 4-n-dodeciloxybenzylidene-4'-cyanoaniline (DOBCA) has been studied by optical microscopy, differential scanning calorimetry, X-ray diffraction and, primarily, by NMR spectroscopy. The smectic phase of the mixture is a partial bilayer smectic A phase (S_Ad), in which about one half of the molecules are associated in pairs through their polar cyano end groups. The molecular dynamics in the smectic A_d phase of the mixture was studied by proton spin-lattice relaxation. Self-diffusion and rotations/reorientations were found to be essential relaxation mechanisms while the contribution of the order director fluctuations seems to be very small in all frequency regions. The correlation times associated with the molecular rotational motion around the short molecular axis, τ_S, are of the order 10^-10 s and the ratio τ_S/τ_L ≈6.2. The translational diffusion coefficients D∥ are of the order 10^-11m²s^-1. The possible contribution to the relaxation rate of an additional relaxation mechanism associated with the dissociation and recombination of molecules in dimers within the smectic layers is also analysed.     

Flow injection analysis methods for determination of diffusion coefficients

Two flow injection analyses (FIA) methods for the determination of diffusion coefficients in a straight single tube FIA system were developed. Based on the analytical solution of the convection-diffusion equation, linear relationships of the logarithmic values of the dispersion coefficient (D) and the half-peak width (W_1/2) with the diffusion coefficient (D_m) were obtained. Experiments were designed to verify these methods. For example, for potassium hexacyanoferrate (III) a D_m value of 0.72 × 10⁵ cm² s⁻¹ was found versus a literature value of 0.76 × 10⁵ cm² s⁻¹ (error, 5%). For potassium hexacyanoferrate (II) a D_m value of 0.67 × 10⁵ cm² s⁻¹ was obtained versus a literature value of 0.63 × 10⁵ cm² s⁻¹ (error, 6%). The diffusion coefficients of some important biomedical compounds, such as dopamine, epinephrine, norepinephrine and ascorbic acid, were then determined. The values of 10⁵ D_m/cm² s⁻¹ are 0.60 ± 0.03, 0.44 ± 0.02, 0.60 ± 0.01 and 0.68 ± 0.06, respectively.     

Director movement and potential function of surface stabilized ferroelectric liquid crystal cells by electrooptical investigations

Electrooptical investigations on a ferroelectric liquid crystal (DOBAMBC) were carried out on a well aligned sample in a 2 μm cell. On the basis of these measurements the complete average director movement during a switching process caused by an electric field can be calculated and will be discussed. The thermodynamic potentials at the S_A*-S_C* phase transition were determined from the experimental results with a modified Landau theory. They serve as a basis for a discussion of the phase transition and the influence of the surface orientation. Some preliminary results were obtained concerning the electrooptical behaviour of the S_H* phase.     

Facilitated transport mechanism in fixed site carrier membranes

Facilitated transport of gases, such as O₂, has been observed for fixed site carrier membranes. Carrier-impregnated ion-exchange membranes have also been used to produce facilitated transport of CO₂, H₂S and olefins when the carriers are not completely mobile. The actual mechanism for this facilitated transport has not been determined previously. The facilitated transport is provided by the exchange of solute between the free solute region and the bound complexing agent combined with gradients in the free solute and complexed carrier. The ratio of mobility for exchange between the regions is the dimensionless equilibrium constant of the reversible reaction. An expression is also derived for the relationship between the effective diffusion coefficient of the complex in facilitated transport, D_AB, and the diffusion coefficients for exchange between free and complexed solute, D_DH and D_HD. Since D_AB can be determined from experimental results, D_DH and D_HD can be calculated. The results also show the morphology dependence of D_AB. The diffusion coefficient of the free solute D_A also changes with the loading of the complexing agent in the film. This morphology dependence can explain why the gas permeability can decrease when the concentration of the complexing agent increases in the membrane.     

An NMR study of translational diffusion and structural anisotropy in magnetically alignable nonionic surfactant mesophases

The diffusion of both water and surfactant components in aqueous solutions of the nonionic surfactant "C12E6"--which includes hexagonal, cubic, lamellar, and micellar mesophases--has been studied by pulsed-field-gradient NMR. Diffusion coefficients were measured in unaligned samples in all of these phases. They were also obtained in the hexagonal and lamellar phases in oriented monodomain samples that were aligned by slow cooling from the micellar phase in an 11.7 T magnet. Measured water and soap diffusion coefficients in the NMR-isotropic cubic and (high-water-content) micellar phases as well as diffusion anisotropy measurements in the magnetically aligned hexagonal phase were quantitatively consistent with the constituent structures of these phases being identical surfactant cylinders, with only the fraction of surface-associated water varying with the water-soap molar ratio. The values of the water and soap diffusion coefficients in the oriented lamellar phase suggest an increase in defects and obstructions to soap diffusion as a function of increasing water content, while those in the low-water-content micellar phase rule out the presence of inverse micelles.     

Application of time-resolved fluorescence in the study of lipid aggregates II. Motions and order of pyrene probes in an aligned lyotropic nematic phase

Time-resolved polarized fluorescence spectroscopy has for the first time, been applied to the study of chromophores in a macroscopically aligned lyotropic nematic phase. The phase is composed of potassium dodecanoate, potassium chloride and water and contains long rod-like aggregates, that are aligned with their long axes parallel to an applied magnetic field. Pyrene, 1-pyrene dodecanoic acid, 1-dodecylpyrene and l-palmitoyl-2-(6-pyrenylhexanoyl)-sn-glycero-3-phosphoryl-choline are solubilized in these aggregates. The photophysics of these probes is a single exponential and typically between 130 and 200 ns in non-degassed samples. For all the probes the plane of the pyrene molecule tends to be oriented perpendicular to the symmetry axis (C_∞ axis) of the aggregate. The order parameters describing the orientation of the electronic transition dipole moment relative to this axis are typically c. -0.05. It is concluded that the translational and the local rotational motions of the probes are fast compared to the fluorescence lifetimes. The correlation times characterizing these motions are shorter than 20 ns. Finally, no slow motions such as fluctuations of the normal to the surface of the rod-like aggregate or a slow wobbling of the C_∞ -axis can be detected during c. 1 μmls.     

Electrical conductivity and cation exchange kinetic studies on poly-o-toluidine Th(IV) phosphate nano-composite cation exchange material

An advanced organic–inorganic cation exchange material poly-o-toluidine Th(IV) phosphate nano-composite was synthesized by a modified sol–gel technique by incorporating Th(IV) phosphate precipitate with the matrix of poly-o-toluidine. The material showed good ion-exchange behavior and used successfully in separation of metal ions. The conductivity of the composite was found within the range of 10⁻² to 10⁻³ S/cm; measured by 4-in-line-probe dc electrical conductivity measuring technique. The conductivity is at the border of metallic and semiconductor region. Ion-exchange kinetics for few divalent metal ions was evaluated by particle diffusion-controlled ion-exchange phenomenon at four different temperatures. The particle diffusion mechanism is confirmed by the linear τ (dimensionless time parameter) versus t (time) plots. The exchange processes thus controlled by the diffusion within the exchanger particle for the systems studies herein. Some physical parameters like self-diffusion coefficient (D₀)_, energy of activation (E_a) and entropy of activation (ΔS⁰) have been evaluated under conditions favoring a particle diffusion-controlled mechanism.     

宏观均相多孔电极电化学阻抗谱基础

电化学阻抗谱可用于诊断多孔电极内电荷转移反应,即界面电荷集聚和电荷传导,以及反应物质输运。本文采用复相量方法,在同态假设条件下,重新推演多孔电极阻抗谱模型,厘清传统多孔电极阻抗谱模型中的模糊性表述。(1) 定义多孔电极表征输入参数,包括电极基体电子电导率σ₁ 、电解质离子电导率σ₂、界面电荷传递电导率g_ct、单位面积界面电容C、固相扩散系数D、速度常数k、电极厚度d、特征孔深L_p 和单位体积表面积S_c;(2) 解析阻抗谱特征输出参数,包括场扩散常数K,特征频率ω₀、ω₁、ω₂、ω₃和 ω_max,它们分别相关于界面传导反应、有限场扩散、氧化还原反应、孔内扩散和最小特征孔尺寸,以及分别对应于从传导到扩散和从扩散到饱和的转折频率f_k1 和f_k2;(3) 当参数X和Z同时变化时(X = σ₁和Z = d,S_c,L_p,C,g_ct,D,k),通过阻抗谱特征参数的演变规律,分析了电荷转移反应中X和Ζ参数耦合竞争;(4)为深入分析电荷转移反应中参数X和Z的耦合竞争,引入了分叉频率f_XZ和f_ZX 。f_XZ和f_ZX所处位置可以用于表征参数X和Z影响电荷转移反应的深度和广度。当分叉频率f_XZ和f_ZX不存在时,表明电荷转移反应中参数X和Z在全频率范围内存在耦合竞争。总之,借助于特征频率和分叉频率,本文一方面研究了动力学参数和微观结构参数对多孔电极中电荷转移反应的影响,另一方面分析谱图的变化及其背后的阻抗谱特征演化规律。本文研究结果可为阻抗谱的系统仿真和辨识提供理论基础,可为多孔电极内电荷转移反应的竞争分析提供技术支撑,还可为电化学储能系统的优化设计提供诊断工具。     

Orientational diffusivities measurement by light-beating spectroscopy for a disk-like thermotropic nematic phase (ND)

Using a light-beating technique and for an appropriate scattering geometry, we have measured separately the orientational diffusivities D_splay and D_twist for an 'hexa-n-alcanoyloxytruxene' (HATX C₁₂H₂₅) sample which exhibits a disk-like thermotropic nematic phase (N_D) between 57°C and 84°C. D_splay and D_twist are about 100 times weaker than those corresponding to rod-like thermotropic nematics. The deviation can be attributed to higher viscosities η_splay and η_twist.     

Dielectric properties of the nematic liquid crystal 4-n-pentyl-4'-cyanobiphenyl in porous membranes

Broadband dielectric spectroscopy (up to 10₉ H_z) is employed to study the molecular dynamics of the liquid crystal 4-n-pentyl-4'-cyanobiphenyl (5CB) in the free bulk phase and confined in cylindrical channels of Anopore membranes having a diameter of 0.2 μm and length of about 60 μm. The bulk samples of 5CB orient almost homeotropically between the untreated metal electrodes of the measurement set-up, and two relaxation processes are observed: the slower δ-relaxation is assigned to hindered rotation (180° flips) of the molecules around their molecular short axis, and a faster second process is attributed to the tumbling of the molecules about this axis. In the confined 5CB samples, the membrane pores align the nematic director axially or radially depending upon their surface preparation. Planar (axial) alignment is always found in untreated membranes, whereas radial alignment was achieved by treatment with decanoic acid. Consequently the director field is fixed perpendicular or parallel to the electric field and we are able to study each of the two relaxation processes separately by appropriate surface treatment of the pores. The frequencies of both processes are found to be unchanged with respect to the bulk phase. We extract the frequency dependence of the dielectric anisotropy δε from the dispersion curves of ε∥ and ε⊥. Two changes of sign of δε = (ε∥-ε⊥) are detected as predicted in the literature.     

On the nematic-nematic phase transition in mixtures composed of sheet-shaped palladium organyls and apolar organic solvents

The three sheet-shaped palladium organyls 1a-c exhibit lyotropic nematic properties in apolar organic solvents. The occurrence of two nematic lyomesophases was verified by the investigation of the orientational properties of these liquid crystalline systems. In cells with obliquely deposited SiO_x layers, the director of the high temperature phase N₂ is aligned in a homogeneous, planar manner. In the low temperature phase N₁, a different orientational pattern is observed. The specific pattern type depends on the deposition conditions of the SiO_x layers. In samples homeotropically aligned in the N₂ phase, the director is tilted away from the cell normal after the transition into the N₁ phase. These changes of orientation are reversible. The experimental observations presented here support our proposed model for the structural change at the nematic-nematic phase transition.     

Measurement of binary diffusion coefficient from impulse response curve having extremely low absorbance intensity under supercritical condition by noise elimination technique

A noise elimination technique was applied to the determination of binary diffusion coefficients D₁₂ from the response curves having extremely low absorbance intensities in impulse response methods under supercritical conditions of carbon dioxide. The effectiveness of this technique was experimentally examined for the analyses of response curves through both the curve-fitting and the moment methods in two cases: the chromatographic impulse response method for phenol and β-carotene with a polymer-coated capillary column, and the Taylor dispersion method for acetone with an uncoated capillary column. Unreliable D₁₂ values were obtained from the moment method of the response curves at lower absorbance intensities, even treated with noise elimination. The curve-fitting method with the noise elimination treatment was quite effective for determining the D₁₂ values accurately, and was valid at the lowest absorbance intensities, on the order of 10⁻⁴ absorbance unit of UV-Vis multi-detector, corresponding to the smallest quantity of the solute, i.e. 6×10⁻⁵, 6×10⁻⁶, and 5×10⁻² μ mol for phenol, β-carotene, and acetone, respectively, under conditions studied. Infinite dilution regions for binary diffusion coefficients were obtained by injecting various amounts: the binary diffusion coefficients showed constant values at concentrations less than 0.6, 0.004, and 0.08 mol m⁻³ for phenol, β-carotene, and acetone, respectively, in supercritical carbon dioxide at 313.2 K and 16–18 MPa.     

The geometry and intermolecular binding of HCN…BrC1 probed by rotational spectroscopy

Ground-state rotational spectra of several isotopomers of a linear complex formed between HCN and BrCl were observed by pulsed-nozzle, F-T microwave spectroscopy and analysed to give the spectroscopic constants B₀, D_J, _χ(Br), _χ(Cl), and M_bb(Br). The order HCN…BrCl of the nuclei was established from the changes in the B₀ values on isotopic substitution. The small fractional electronic charge (δ ≈ 0.05) transferred from Br to Cl on complex formation and the intermolecular stretching force constant (k_σ ≈ 11 N m⁻¹) estimated from the spectroscopic constants indicates a weak interaction of HCN and BrCl, with little perturbation of the charge distribution of BrCl.     

Infrared study of the rotational diffusion of allene in carbon sulfide

The profiles of the parallel and perpendicular bands ν₆ and ν₁₀ of allene in CS₂ and their temperature dependence have been studied. These profiles are sensibly lorentzian and consequently allow us to derive the components D and D of the rotational diffusion tensor and the corresponding activation energies; the accuracy of the results is discussed. In particular, it is not possible to determine unambiguously whether the activation energies U_| and U are equal or different but, whichever the case, the ratio D/D is of the order of 10. An application test of the extended J rotational diffusion model shows that the results concurrently obtained for the ν₆ and ν₁₀ bands are incompatible with this model and we come to the conclusion that the rotation of allene about its various axes is anisotropic.     

Surface diffusion in reversed-phase liquid chromatography using silica gels bonded with C1 and C18 ligands of different densities

Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C₁ and C₁₈ alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (D_s) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C₁ and C₁₈ ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate D_s values under various RPLC conditions. The D_s values can be estimated with a mean square deviation of about 25–30%. The agreement between the D_s values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C₁ and C₁₈ ligands and that the contribution of each ligand is proportional to the ligand density.     

Sulfonated poly(arylene ether sulfone) ionomers containing fluorenyl groups for fuel cell applications

A series of sulfonated poly(arylene ether sulfone)s (SPEs) containing fluorenyl groups as bulky components were synthesized and characterized for fuel cell applications. Introduction of disodium 3,3′-disulfo-4,4′-difluorophenyl sulfone (SFPS) monomer gave ionomers with high acidity and accordingly high proton conductivity as well as high proton diffusion coefficient (D_σ) at low humidity. The membrane of SPE60 (where the number denotes mole percentage of the component containing sulfonic acid groups; IEC (ion exchange capacity) = 1.68 mequiv./g) exhibited high proton conductivity of 4.6 × 10⁻³ S/cm at 40% RH and 80 °C, which is one order of magnitude higher than that (6 × 10⁻⁴ S/cm) of our previous SPE (SPE-1, IEC = 1.58 mequiv./g). D_σ of SPE60 membrane was ca. 4 times higher than that of the SPE-1 membrane at low water volume fraction. SPE membranes showed good oxidative and hydrolytic stability as well as favorable thermal and mechanical properties. Small-angle X-ray scattering analyses showed that the phase separation of SPE membranes was much less developed than that of the perfluorinated Nafion membrane which accounts for lower hydrogen and oxygen permeability of the former membranes.