首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 640 毫秒
1.
We focused to highlight the effect of quenching on the development and ordering of non-aqueous lyotropic liquid crystalline phases. Lyotropic mesophases are prepared from binary mixtures of sodium dodecyl sulphate and ethylene glycol at varying concentrations 30:70 and 50:50 wt%. The obtained self-assembled phases are characterised by X-ray diffraction, polarisation optical microscopy, differential scanning calorimetry and dielectric spectroscopy to evaluate the structural, optical, thermal and dielectric behaviours. Structural and textural measurements confirmed mesomorphic and crystalline phases for both mixtures. Calorimetric study gives insight about the growth of new phases at ≈335 K and isotropic temperatures of these mixtures. Both the mixtures are quenched from 335 K to the 303 K to analyse the effect of quenching on the structure and ordering of mesophases. We noticed well-defined hexagonal liquid crystalline mesophases for both concentrations after quenching at 303 K. Dielectric and relaxation behaviours of quenched mesophases were also examined. Higher capacitance and dielectric strength are noticed for quenched mixtures. The application prospective of such phases is also discussed.  相似文献   

2.
The investigation addressed in the title was carried out on a total of 17 members of the two disc-shaped series 1 or 2 of radial hexaesters differing only in their cyclic C6-core units. Their lyotropic behaviour appeared to be dependent on the intracolumnar order of stacking of the respective hexaester molecules. With linear alkanes in mixtures with the phenylene centred hexaesters (series 1 derived from hexahydroxybenzene) no lyomesomorphism occurs, whereas with most of the cyclohexane centred analogues (series 2, scyllitol derivatives) even two lyomesophases were observed: a hexagonal type and, in 49 cases, a nematic columnar (induced) phase. Here, the lyotropy demonstrates its dependence on the length of chains both of the alkanoyl groups of 2 and the solvent (the linear alkanes) used. In the case of the selected cyclic solvents, three factors proved to govern the lyotropic mesomorphism of all these disc-like hexaesters: (1) their degree of saturation, (2) their molecular size/volume, and (3) their stereostructure. Interestingly, with benzene and other (less unsaturated) monocyclic solvents, both series of hexaesters exhibit only a hexagonal type of mesophase which is induced in four cases. Saturated monocyclic hydrocarbons act on members of the aromatic centred series 1 in the same way; with cyclohexane however, two more cases of induction of a hexagonal type of lyomesophase have been observed. To our surprise, binary mixtures of most hexaesters of series 2 (scyllitol derivatives) with saturated monocyclic hydrocarbons show the same polymorphic (nematic and hexagonal) situation as that found here with linear hydrocarbons; moreover, in comparison with the results with linear alkanes, four more cases of induced phases appear with these cycloalkanes. These results, in particular the many cases of lyomesophase induction, relate to the first examples of lyotropic mesomorphism in binary systems of disc-like materials with saturated cyclic solvents/hydrocarbons. Finally, in some examples presented here it was found for the first time that bulkiness/space-filling or the stereostructure of the saturated cyclic solvents/hydrocarbons, e.g. cis- or trans-decalin, also play an important role in the lyotropic mesomorphism of their mixtures with the radial hexaesters of the two series 1 and 2. By means of models shown here for the first time in figures 4 to 6, ideas are put forward about peculiarities due to microsegregation in relation to the (formally) very similar members of both hexaester series 1 and 2 as a key to understanding the drastic difference in their thermotropic as well as their lyotropic states.  相似文献   

3.
《Liquid crystals》1999,26(12):1723-1734
The investigation addressed in the title was carried out on a total of 17 members of the two disc-shaped series 1 or 2 of radial hexaesters differing only in their cyclic C6-core units. Their lyotropic behaviour appeared to be dependent on the intracolumnar order of stacking of the respective hexaester molecules. With linear alkanes in mixtures with the phenylene centred hexaesters (series 1 derived from hexahydroxybenzene) no lyomesomorphism occurs, whereas with most of the cyclohexane centred analogues (series 2 , scyllitol derivatives) even two lyomesophases were observed: a hexagonal type and, in 49 cases, a nematic columnar (induced) phase. Here, the lyotropy demonstrates its dependence on the length of chains both of the alkanoyl groups of 2 and the solvent (the linear alkanes) used. In the case of the selected cyclic solvents, three factors proved to govern the lyotropic mesomorphism of all these disc-like hexaesters: (1) their degree of saturation, (2) their molecular size/volume, and (3) their stereostructure. Interestingly, with benzene and other (less unsaturated) monocyclic solvents, both series of hexaesters exhibit only a hexagonal type of mesophase which is induced in four cases. Saturated monocyclic hydrocarbons act on members of the aromatic centred series 1 in the same way; with cyclohexane however, two more cases of induction of a hexagonal type of lyomesophase have been observed. To our surprise, binary mixtures of most hexaesters of series 2 (scyllitol derivatives) with saturated monocyclic hydrocarbons show the same polymorphic (nematic and hexagonal) situation as that found here with linear hydrocarbons; moreover, in comparison with the results with linear alkanes, four more cases of induced phases appear with these cycloalkanes. These results, in particular the many cases of lyomesophase induction, relate to the first examples of lyotropic mesomorphism in binary systems of disc-like materials with saturated cyclic solvents/hydrocarbons. Finally, in some examples presented here it was found for the first time that bulkiness/space-filling or the stereostructure of the saturated cyclic solvents/hydrocarbons, e.g. cis- or trans-decalin, also play an important role in the lyotropic mesomorphism of their mixtures with the radial hexaesters of the two series 1 and 2. By means of models shown here for the first time in figures 4 to 6, ideas are put forward about peculiarities due to microsegregation in relation to the (formally) very similar members of both hexaester series 1 and 2 as a key to understanding the drastic difference in their thermotropic as well as their lyotropic states.  相似文献   

4.
Rigid, helical polyisocyanodipeptides derived from alanine (PIAAs) that form lyotropic liquid‐crystalline (LC) phases in tetrachloroethane are presented. An investigation by optical microscopy between crossed polarizers demonstrated that PIAAs prepared by the polymerization of isocyanodipeptide monomers with an activated tetrakis isocyanide nickel(II) catalyst could form cholesteric LC phases in tetrachloroethane in concentrations between 18 and 30 wt %. Cholesteric LC phases that were formed in solutions of greater than 25 wt % displayed a reversal of the cholesteric helix upon annealing at 50 °C. Diastereomeric PIAA mixtures displayed cholesteric LC behavior only when the PIAAs had the same helix screw sense. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 981–988, 2007  相似文献   

5.
Variable-temperature proton magnetic relaxation dispersion (PMRD) profiles are collected in the induced nematic phases of the binary liquid crystalline mixtures composed of smectic mesogens: 5-butyl-2-(4-isothiocyanatophenyl)-1,3-dioxane (4DBT) and 4′-dodecyl-4-cyanobiphenyl (12CB) and the low viscous nematogen 4-(trans-4′-n-hexylcyclohexyl)-isothiocyanatobenzene (6CHBT), with a view to assess the influence of local organisations on the power spectrum of director fluctuation modes. Two distinct compositions of the binary mixture i.e. 50 mol% of 12CB (without a smectic phase) and 70 mol% of 12CB (with a smectic phase) are used. Fast Field Cycling nuclear magnetic resonance relaxometry is employed to measure proton spin-lattice relaxation rates (R1) as a function of Larmor frequency (10 kHz–30 MHz). PMRD data analysis with the choice of a suitable model indicated nematic clusters of moderate size (~200 Å) found in the broad nematic region of 50 mol% 12CB, whose size is almost invariant with temperature. On the other hand, cybotactic clusters, i.e. local smectic organisations of relatively larger size (~2000–3000 Å), are observed near the nematic–smectic transition (T > TAN) of 70 mol% 12CB. Interestingly, the shape geometry of such local organisations accessed from PMRD analysis is weakly anisotropic near TAN, while being isotropic near TNI for 70 mol% 12CB.  相似文献   

6.
This study highlights the effects of amphiphile chain length and counter ions on the self-assembly and dielectric behaviour of non-aqueous lyotropic liquid crystals. Two-dimensional hexagonal mesophase is seen for short-chain length sodium dodecyl sulphate, while lamellar and multiwall lamellar mesophases are noticed for long-chain length cetyltrimethylammonium bromide and polyoxyethylene (20) sorbitan monolaurate amphiphiles in the non-aqueous domains of ethylene glycol. A strong influence of amphiphile counter ions is seen on static dielectric constant, loss factor, relaxation frequency and relaxation time of these lyotropic mixtures. Refractive indices of these lyotropic phases are also highlighted.  相似文献   

7.
Thermodynamical, optical, and electrical properties of the binary mixtures of cholesteryl myristate (ChM) and 4-n-decyloxybenzoic acid (DOBA) have been carried out by the differential scanning calorimeter, polarized optical microscopy (POM), and impedance spectroscopy. Through thermodynamic study, various phase transition temperatures, transition enthalpies, and transition entropies have been determined to investigate temperature range and stability of the mesophases of the mixtures. Phase diagrams in the heating and cooling cycles have been drawn for the ChM–DOBA binary system. Optical textures of different mesophases have identified with the help of POM. Dielectric permittivity has been determined in planar and homeotropic alignments of the mixtures having DOBA concentrations 30.0 and 92.3 mol %. The experimental dielectric data in the frequency range of 1 Hz to 35 MHz do not show any relaxation mode in both the alignments of these mixtures. Dielectric anisotropy has been determined for the various observed phases of the mixtures.  相似文献   

8.
Supramolecular liquid crystalline complexes were obtained from binary mixtures of 3‐(4‐pyridyl)‐5‐(4‐n‐alkoxy)phenyl‐1,2,4‐oxadiazoles and 2,5‐thiophene dicarboxylic acid. Although the oxadiazole derivatives and the dicarboxylic acid are non‐mesomorphic, the H‐bonded complexes exhibit mesomorphism. Their liquid crystalline properties were investigated by differential scanning calorimetry and polarizing optical microscopy. The complexes exhibit enantiotropic nematic phases. A structural study involving AM1 semi‐empirical calculations is also described.  相似文献   

9.
Supramolecular liquid crystalline complexes were obtained from binary mixtures of 3-(4-pyridyl)-5-(4-n-alkoxy)phenyl-1,2,4-oxadiazoles and 2,5-thiophene dicarboxylic acid. Although the oxadiazole derivatives and the dicarboxylic acid are non-mesomorphic, the H-bonded complexes exhibit mesomorphism. Their liquid crystalline properties were investigated by differential scanning calorimetry and polarizing optical microscopy. The complexes exhibit enantiotropic nematic phases. A structural study involving AM1 semi-empirical calculations is also described.  相似文献   

10.
ABSTRACT

Two novel trimethacrylates, i.e., 1,1,1-tri-[4-(methacryloxyethoxy)-phenyl] ethane (TMPE) and 1,1,1-tri-[4-(2-methyl-2-methacryloxyethoxy)-phenyl]ethane (TMMPE), have been synthesized by reacting methacryloyl chloride with the corresponding hydroxyl intermediates. Both trimethacrylate monomers, having a low viscosity of 11.5 and 13.1 Pa.S, respectively, were blended with TEGDMA at three different weight ratios, i.e., 90/10, 70/30, and 50/50. The mixtures were made visible light-curable (VLC) by the addition of camphorquinone (0.5 wt%) and N,N-dimethyl-aminoethyl methacrylate (1.0 wt%). In addition to evaluation as cured neat resins, VLC formulations with 70% by wt. of silanated microfiller were also prepared and evaluated. The control in both cases was a VLC formulation of BisGMA/TEGDMA (70/30 and 50/50 wt/wt). These new, formulated resins have both improved physical properties and higher double bond conversion than the BisGMA control, as well as decreased linear polymerization shrinkage (LPS). The neat resin having 70/30 (wt/wt) ratio of TMPE/TEGDMA (T7T3, Table 2) exhibited a compressive strength (CS) of 496 (±51) MPa compared to the 70/30 (wt/wt) ratio of BisGMA/-TEGDMA control having 425(±27) MPa. A filled resin having a 90/10 (wt/wt) ratio of TMPE/TEGDMA exhibited a flexural strength (FS) of 122.6(±23) MPa, compared with a similar filled BisGMA/TEGDMA (70/30, wt/wt) resin exhibiting 112.7(±19) MPa. These and other results suggest that these new trimethacrylates have potential application in formulating dental composites with improved performance.  相似文献   

11.
Abstract

Dielectric relaxation of water molecules in the lamellar, Lα, cubic and hexagonal, Hα, lyotropic structures of nonylphenoxy-poly(ethylenoxy)ethanol (Ark. 9) has been studied by dielectric time domain spectroscopy in the frequency range between 10 MHz and 10 GHz. The values of the relaxation times, obtained at room temperature, are the following: 41 ps for the Lα phase, 29 ps for the cubic phase and 22 ps for the Hα phase. As is seen, the relaxation time of bound water is distinctly higher than that of pure water, and it depends strongly on the phase structure. The relaxation times measured for the liquid-crystalline phases as well as for pure Ark. 9 obey the Arrhenius law, and the energy barriers obtained have the following values: (20 ± 2) kJ/mol for all the liquid-crystalline phases, and (30 ± 3) kJ/mol for pure Ark. 9. The former is in good agreement with the value found for bound water in lipid systems whereas the latter is characteristic of the isotropic phase of thermotropic liquid crystals.  相似文献   

12.
Andrey Kuzmin 《Liquid crystals》2013,40(7):1024-1027
The electrical conductivity of dodecylbenzenesulphonate (DoBS) ionic lyotropic liquid crystal of the systems: LiDoBS (dodecylbenzenesulphonic acid lithium salt)/water, NaDoBS (dodecylbenzenesulphonic acid sodium salt)/water, and KDoBS (dodecylbenzenesulphonic acid potassium salt)/water were investigated by impedance spectroscopy in the frequency range from 0.5 Hz to 0.5 MHz. The electrical conductivity of lyotropic LiDoBS was higher than that of isotropic phase. The electrical conductivity isotropic KDoBS and NaDoBS was higher than the conductivity of lyotropic ones. The temperature dependence of electrical conductivity was investigated in the systems LiDoBS/water and KDoBS/water for different phases. The activation energy of electrical conductivity is lowest for the normal hexagonal phase LiDoBS/water. Such systems based on anionic surfactants are of interest as the electrolyte for the supercapacitors.  相似文献   

13.
The dielectric complex spectra of 2-nitrotoluene with primary or secondary alcohol binary mixtures were studied over the frequency range of 10 MHz to 20 GHz for the whole solute mole fraction range at four different temperatures. An unusual suppression phenomenon was observed in the real and imaginary parts of the mixture complex spectrum, which are smaller than those for the pure alcohols, at low solute concentrations. The dielectric constant and dielectric relaxation time values were obtained by fitting the complex dielectric spectrum data to the single Debye model using a non-linear least squares method. The dielectric constant of mixtures decrease with the increasing mole fraction of 2NT in both the primary alcohols and secondary alcohols; the dielectric relaxation time decreases for all the five binary systems. Using the dielectric data, derived dielectric parameters, namely: the excess dielectric constant, excess inverse relaxation time, effective Kirkwood correlation factor, molar activation enthalpy and molar activation entropy, were calculated. The non-linear variation of permittivity (?0) reveals the change in size and shape of hetero-molecular complex due to intermolecular H-bond interaction. The negative variation of the excess permittivity constant confirms that the dipoles form multimer structures with anti-parallel ordering of unlike dipoles. The molar activation enthalpy was found to be higher at 0.2 mol fraction of 2NT for primary alcohol binary system. To confirm the molecular function group interaction, a FT-IR spectroscopy study was carried out at 298 K. The FT-IR analysis confirmed the formation of hydrogen bonds between the hydrogen atom of hydroxyl groups of the alcohols and the oxygen atom of nitro groups of 2NT in the binary mixtures.  相似文献   

14.
Analogously to aqueous K-soap/water systems already examined, the glycerol-containing systems KC n /G (KC n ;n=12, 14, 16, 18, 22; G=glycerol) are also able to build up hexagonal, lamellar, optically isotropic, gel-like and crystalline phases. These preliminary phases have been identified by texture observations of contact samples and singular concentrations with a polarizing microscope. The appertaining phase regions have been plotted in the binary phase diagrams.Correspondences and differences between these systems have been elucidared by drawing a comparison. Mosaic texture and oily streaks are typical of the lamellar phase. Spherulites are mainly found in the heterogeneous two-phase region lamellar/isotropic. The textures of the hexagonal phase are of fan-like morphology. The appearance of the gel phase texture resembles globular or curd-like structures.The influences exerted by the increasing chain lengths of the K-soaps (KC n ,n=12–22) on the phase regions in the binary systems (KC n /G) can be described as follows. The concentrations required for forming the hexagonal and the lamellar phase respectively are shifted toward lower K-soap concentrations. The concentration range in which the hexagonal phase is stable is diminished. The temperature range in which the hexagonal phase is stable becomes larger. The upper temperature limit of the lamellar phase region is lowered.Binary aqueous and glycerol-containing K-soap systems have the following common features: The hexagonal phase is built up at low soap concentrations. The lamellar phase is formed at high soap concentrations. The lamellar phase is formed at high soap concentrations. An optically isotropic region is inserved between the lamellar and the hexagonal phase in aqueous and glycerol-containing systems of the types KC14, KC16 and KC18. The temperature of the transition hexagonalisotropic phase (HS) runs through a maximum value. On increasing the chain length the formation of the hexagonal phase is shifted in the direction of lower soap concentrations.Aqueous and glycerol-containing K-soap mixtures differ in the following essential points: The lyotropic mesophases (H, L, I) of aqueous systems are formed at considerably lower soap concentrations than the corresponding phases of glycerol-containing systems. The lamellar phases of aqueous systems reach the regions of very low soap concentrations. The lyotropic mesophases of aqueous systems are built up at temperatures lower than the corresponding ones of glycerol-containing mixtures. In aqueous systems the concentration range of the lamellar phase increases with increasing chain length, in contrast to glycerol-containing systems where it is diminished.  相似文献   

15.
《Liquid crystals》2012,39(13-14):1973-1984
ABSTRACT

Star-shaped nonaalkoxy-1,3,5-triphenyltriazines were prepared and their mesomorphism was investigated by differential scanning calorimetry (DSC), polarised optical microscopy (POM) and X-ray diffraction (WAXS and SAXS). Compounds with chain lengths C9 – C12 displayed enantiotropic hexagonal columnar mesophases over a wide range of temperature. Their similarity in molecular size and mesomorphism prompted us to study their binary mixtures with previously reported planar 1,3,5-triphenylboroxines and propeller-shaped 1,3,5-triphenylbenzenes. All three compounds are fully miscible in their hexagonal columnar mesophases, but mixtures of planar with propeller-shaped compounds generated columnar stacks that contain only one type of molecule to avoid their shape incompatibility. However, the two types of columnar stacks were fully miscible which circumvented macroscopic phase separation.  相似文献   

16.
The solution‐phase behavior of three main‐chain viologen polymers, which are composed of isomeric xylyl units and triflimide as a counterion, was studied in methanol, dimethylformamide, acetonitrile, and dimethyl sulfoxide as solvents microscopically under crossed polarizers. Each of them exhibited a lyotropic lamellar phase in both polar protic and aprotic solvents. Their C* for the formation of biphasic solutions (1–5 wt %) and concentrations (20–30 wt %) for the lyotropic solutions in methanol was much lower than those in polar aprotic solvents (20–71 and 60–81 wt %, respectively). Their high solubility, high C* for the formation of biphasic solutions, and high concentrations for the formation of lyotropic solutions in polar aprotic solvents were related to the significant reduction of strong ionic interactions between triflimide and 4,4′‐bipyridinium ions in each of these viologen polymers. They were the first examples of viologen polymers that exhibited a lyotropic phase in polar aprotic solvents. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2015–2024, 2002  相似文献   

17.
The low frequency relaxation process was studied for 6OCB/8OCB mixtures with three concentrations (27.0, 27.3 and 27.5 wt %) exhibiting the isotropic-nematic-smectic A-nematic re-entrant-crystalline phase sequence and four mixtures (28.5, 30.0, 35.0 and 40.0 wt %) with the isotropic-nematic-crystalline phase sequence. In the liquid crystalline phases, all dielectric spectra could be excellently described by the Debye equation. The relaxation time tau passes smoothly through the phase transitions separating the liquid crystalline phases. The activation barriers hindering the molecular rotations around the short axes are practically the same in the nematic and smectic phases and become larger in the re-entrant nematic phase. Smaller values of the barrier in the nematic phase of mixtures in comparison with those obtained recently for pure 6OCB and 8OCB are explained as an effect of weakening of the molecular interactions caused by increased dipole-dipole associations between molecules in mixtures in relation to pure substances. The slightly larger activation barrier in the nematic re-entrant phase indicates stronger molecular associations in this phase. d  相似文献   

18.
《Liquid crystals》2000,27(12):1675-1681
The low frequency relaxation process was studied for 6OCB/8OCB mixtures with three concentrations (27.0, 27.3 and 27.5 wt %) exhibiting the isotropic-nematic-smectic A-nematic re-entrant-crystalline phase sequence and four mixtures (28.5, 30.0, 35.0 and 40.0 wt %) with the isotropic-nematic-crystalline phase sequence. In the liquid crystalline phases, all dielectric spectra could be excellently described by the Debye equation. The relaxation time tau passes smoothly through the phase transitions separating the liquid crystalline phases. The activation barriers hindering the molecular rotations around the short axes are practically the same in the nematic and smectic phases and become larger in the re-entrant nematic phase. Smaller values of the barrier in the nematic phase of mixtures in comparison with those obtained recently for pure 6OCB and 8OCB are explained as an effect of weakening of the molecular interactions caused by increased dipole-dipole associations between molecules in mixtures in relation to pure substances. The slightly larger activation barrier in the nematic re-entrant phase indicates stronger molecular associations in this phase. d  相似文献   

19.
A RP-LC method is presented, which is sensitive and selective for the simultaneous determination of enalapril–lercanidipine and enalapril–nitrendipine binary mixtures in their pharmaceutical dosage forms. The analyte peaks were detected using the LC method with the mobile phase ratio of methanol: water (70:30 v/v, pH 3.0) and a 1.0 mL min?1 flow rate. The detection wavelength was selected at 210 nm using photo diode array detector and column temperature was optimized to 30 °C. Linearity was obtained at different concentration ranges for all working pharmaceutically active compounds between 0.5 and 25 μg mL?1. The proposed methods were extensively validated according to USP 27 requirements and ICH guidelines. The methods were applied to the analysis of pharmaceutical dosage forms containing binary mixtures of enalapril–lercanidipine and enalapril–nitrendipine. Moreover, the proposed methods were applied for the degradation studies of the selected compounds. Degradation studies were conducted using stress conditions such as UV light, acidic and alkaline hydrolysis, oxidation and heat in oven, to evaluate the ability of the separation of the response of standard compounds from their degradation products.  相似文献   

20.
The polymerisation of styrene in lyotropic liquid-crystalline (LC) phases of dioctadecyldimethylammonium bromide (DODAB) in water is explored. Amphiphile concentrations between 20 and 50 wt % are employed. The study is set out as a model study for polymerisation reactions in nonstabilised, nonfunctional bilayer systems. X-ray characterisation was used to assess the phase behaviour of the lyotropic mesophases before, during and after polymerisation. The DODAB/water system forms the lamellar phase within the concentration range considered. Addition of styrene to the lamellar phase of DODAB at an equimolar ratio induces a phase shift to a bicontinuous cubic phase at elevated temperatures near the phase-transition temperature. Upon polymerisation within this cubic phase, the phase structure is maintained if the system is kept at constant temperature; however, if the polymer/amphiphile phase is cooled, the lamellar phase, being typical of the DODAB/water system, is restored. It is concluded that, as a result of phase separation between the polymer and the amphiphile phase, the polymerisation in lyotropic LC phases does not provide a stable copy of the templating amphiphile phase. This is in analogy to the observations for polymerisations in other lyotropic phases. Received: 16 March 2000 Accepted: 1 July 2000  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号