热致液晶高分子微纤的形貌特征和一个模量分析的方法

热致液晶高分子微纤的形貌特征和一个模量分析的方法益小苏，沈烈（浙江大学高分子科学与工程学系，杭州，３１００２７）关键词热致液晶高分子，原位复合，弹性模量，注塑由于主链型热致液晶高分子（ＬＣＰ）的高模量、高强度、易取向、低粘度等特性，当将这种高分子以较...     

线型光敏聚酯制备液晶光控取向膜

线型光敏聚酯制备液晶光控取向膜;线型聚酯;液晶;光控取向;光敏高分子     

柔性高分子/小分子液晶混合物的自洽场理论

发展了柔性高分子/小分子液晶混合物连续自洽场理论，将小分子液晶模型化 为取向与位置无关的单体分子，小分子液晶间存在各向异性的Maier-Saupe相互作 用，该理论可还原成高分子和各向同性小分子组成的Flory-Huggins溶液理论和纯 液晶的Maier-Squpe液晶理论，通过数值解自洽场方程组，还将理论用于研究柔性 高分子/小分子液晶混合物相分离开界面性质，得到的结果与用Helfand格子界面理 论和MOnte Carlo模拟的结果一致。     

手征性侧链液晶高分子取向结构的研究

用偏光显微镜,红外二色性和Ｘ 射线衍射研究了一种手征性侧链液晶高分子的相态织构和弛豫行为．偏光显微镜观察这种侧链液晶高分子冻结取向液晶态薄膜时,可观察到与剪切方向垂直的明暗相间的条带织构．红外二向色性的结果表明,取向态中侧链上的介晶基元倾向于与剪切方向垂直排列．取向和非取向膜的Ｘ射线衍射揭示了该侧链液晶高分子具有反铁电性液晶的两套反相螺旋结构．取向薄膜在液晶态的弛豫行为表明,取向作用能促进侧链高分子近晶相层状结构的生长,而且介晶基元的取向在弛豫过程中能保持下来．     

甲壳型液晶高分子的构筑、自组装及其功能化

甲壳型液晶高分子的发展很大程度上依赖于聚合物自组装的发展,而各种可设计、可预测、可调控的自组装策略的涌现,将甲壳型液晶高分子研究推向前所未有的高度,同时也极大地丰富了高分子化学与物理的内容,提升了研究水准.研究表明,侧链"甲壳效应"在调控甲壳型液晶高分子有序结构等方面有着重要作用.本综述从甲壳型液晶高分子设计合成、液晶相态调控、嵌段共聚物自组装和功能化应用等方面,总结和评述了近年来该领域国内的最新研究进展.最后,本综述总结了甲壳型液晶高分子在发展中所面临的主要问题,并对其发展趋势进行了展望.     

室温光致形变主链型交联液晶高分子纤维执行器

将分别含有偶氮苯和苯甲酸苯酯的2种液晶单体与伯胺进行迈克尔加成反应,得到分子量可控的主链型液晶低聚物.利用先熔融提拉、后自由基聚合的方法将低聚物制备成交联液晶高分子纤维.液晶单体与伯胺之间的扩链反应有效地降低了高分子网络的交联密度,进而降低纤维的玻璃化转变温度.同时,这种先拉伸、再聚合的方式将纤维的取向与交联过程分开,保证了纤维中的液晶基元沿拉伸方向呈规整排列.因此,取向后的交联液晶高分子纤维可在室温下实现可逆光致弯曲形变,其最大弯曲角度接近60°,且弯曲方向可以通过改变光照方向进行调控.这种形变幅度大、方向可控的主链型交联液晶高分子纤维有望推动光响应柔性执行器等领域的发展.     

聚对氧化偶氮苯酚酯系列热致性液晶高分子的合成及液晶态研究

本文用界面缩聚法合成聚对氧化偶氧苯酚酯系列热致性液晶高分子。并用DSC,X-光衍射和偏光显微镜对其结构和液晶相进行了表征与研究。观察液晶态织态结构,计算液晶态时分子链间距,并观察聚合物取向液晶态的结晶结构。     

分子模拟在高性能聚合物纤维力学性能研究中应用

聚合物力学性能取决于单个分子链的力学性质和分子链聚集形态。综述了通过分子模拟研究高度取向的液晶高分子纤维的微观力学行为,从微观角度揭示聚合物力学性能的本质,解释其力学破坏的结构因素。     

响应性交联液晶高分子仿生致动器的研究进展

交联液晶高分子兼具液晶取向有序性和交联聚合物熵弹性等特点,能够以动态可调节和可逆的方式来模仿生物体的行为,在仿生器件、柔性机器人、智能表面、生物医药等领域具有良好的应用前景.本综述总结了近几年智能响应性交联液晶高分子在仿生致动器方面的研究进展,从响应性交联液晶高分子的结构和驱动机理出发,讨论了响应性交联液晶高分子的合成工艺、制备技术和成型方法,以及响应性交联液晶高分子对光、热、磁、湿度的响应.此外,介绍了响应性交联液晶高分子致动器在柔性机器人、人工肌肉、微流体运输等领域的应用.最后,对响应性交联液晶高分子的发展前景进行了展望.这项工作主要讨论了响应性交联液晶高分子,旨在为具有新颖功能和更有挑战性的智能微型致动器提供新的设计思路.     

高分子液晶向列相的向错结构

高分子液晶态向错结构在正交偏振片下呈现出具有不同数目黑刷子的纹影织构，是由于分子指向矢取向排列上的不连续性所引起的一种光学效应。近年来，高分子液晶态向错结构的研究已取得了较大进展，发展和应用片晶装饰、条带织构装饰和表面裂纹装饰等技术可以在电镜和偏光显微镜下直接观察各种向错结构。本文简要介绍高分子液晶态向列相的向错和反转壁结构的几何学、高强度向错以及近年在实验上观察各类型向错形态的研究进展。     

Photochromic hybrid organic-inorganic liquid-crystalline materials built from nonionic surfactants and polyoxometalates: elaboration and structural study

This work reports the elaboration and structural study of new hybrid organic-inorganic materials constructed via the coupling of liquid-crystalline nonionic surfactants and polyoxometalates (POMs). X-ray scattering and polarized light microscopy demonstrate that these hybrid materials, highly loaded with POMs (up to 18 wt %), are nanocomposites of liquid-crystalline lamellar structure (Lalpha), with viscoelastic properties close to those of gels. The interpretation of X-ray scattering data strongly suggests that the POMs are located close to the terminal -OH groups of the nonionic surfactants, within the aqueous sublayers. Moreover, these materials exhibit a reversible photochromism associated to the photoreduction of the polyanion. The photoinduced mixed-valence behavior has been characterized through ESR and UV-visible-near-IR spectroscopies that demonstrate the presence of W(V) metal cations and of the characteristic intervalence charge transfer band in the near-IR region, respectively. These hybrid nanocomposites exhibit optical properties that may be useful for applications involving UV-light-sensitive coatings or liquid-crystal-based photochromic switches. From a more fundamental point of view, these hybrid materials should be very helpful models for the study of both the static and dynamic properties of nano-objects confined within soft lamellar structures.     

A chiral induced ferroelectric liquid crystal phase transition with a vanishingly small enthalpy

Information on molecular interactions that give rise to the stabilization of various ferroelectric, liquid-crystalline mesophases is important to the realization of their potential utility in a wide variety of optical devices. Understanding the roles that optical activity and optical purity play in the formation and properties of the various smectic phases is therefore of particular interest. In order to study this relationship three new liquid-crystalline materials were prepared, one as a racemic mixture, the other two as the optically active analogues. The optically active isomers appear to exhibit a different mesophase morphology from the racemate. The chiral compounds apparently possess two extra ferroelectric mesophases in comparison to the racemic mixture. The transitions to and from these phases have extremely small enthalpies. An attempt is made to explain the results for the chiral compounds in terms of differing dipolar couplings in the chiral ferroelectric phases. In the racemic mixture these interactions are compromised or scrambled by a loss of asymmetry thus destabilizing these extra phases.     

Photoluminescence of nanocomposites of liquid-crystalline polymers and cadmium selenide quantum dots

The role of specific interactions between a polymer matrix and incorporated quantum dots is one of the critical problems for understanding the effect of the polymer matrix on the optical properties of quantum dots in a nanocomposite material and for creating new photonic materials and related instruments. In this study, cadmium selenide quantum dots have been incorporated into a liquid-crystalline polymer via the interaction of carboxyl groups of the polymer with the quantum-dot surfaces through ionic bonds. From the data of transmission electron microscopy, it has been shown that this interaction provides the localization of quantum dots in the environment of the liquid-crystalline phase of the polymer. Various features of photoluminescent properties have been observed and interpreted in terms of the emission recombination of excitons in CdSe quantum dots, light reabsorption by quantum dots, the effect of the electronic states on the surface CdSe-liquid crystal, and the energy transfer from quantum dots to the polymer liquid-crystalline matrix.     

A chiral induced ferroelectric liquid crystal phase transition with a vanishingly small enthalpy

Abstract

Information on molecular interactions that give rise to the stabilization of various ferroelectric, liquid-crystalline mesophases is important to the realization of their potential utility in a wide variety of optical devices. Understanding the roles that optical activity and optical purity play in the formation and properties of the various smectic phases is therefore of particular interest. In order to study this relationship three new liquid-crystalline materials were prepared, one as a racemic mixture, the other two as the optically active analogues. The optically active isomers appear to exhibit a different mesophase morphology from the racemate. The chiral compounds apparently possess two extra ferroelectric mesophases in comparison to the racemic mixture. The transitions to and from these phases have extremely small enthalpies. An attempt is made to explain the results for the chiral compounds in terms of differing dipolar couplings in the chiral ferroelectric phases. In the racemic mixture these interactions are compromised or scrambled by a loss of asymmetry thus destabilizing these extra phases.     

Influence of polar dopant on internal configuration of azoxybenzene nematic-in-water droplets

We report the study of optical textures and director configurations within nematic-in-water microdroplets of the liquid-crystalline mixtures based on azoxybenzene and cyanobiphenyl (as a polar dopant). Both pure azoxybenzene and polar dopant materials exhibited bipolar configuration within liquid-crystalline droplets, whereas their mixtures at appropriate concentrations spontaneously formed radial droplets. It was found that increasing of the dopant’s concentration resulted in the forward tangential-homeotropic and reentrant homeotropic-tangential anchoring transitions. We also triggered bipolar-to-radial structural transition by UV irradiation providing trans-cis isomerisation of nematogens. Critical irradiation time needed for radial configuration formation was found to decrease with concentration of polar dopant. Mesoscoping modelling is proposed to explain main experimental results. The presented data are discussed for chemical and biological sensing applications.     

Highly photoluminescent polyoxometaloeuropate-surfactant complexes by ionic self-assembly

Facile organization of the inorganic sandwiched heteropolytungstomolybdate K13[Eu(SiW9Mo2O39)2] (E) into highly ordered supramolecular nanostructured materials by complexation with a series of cationic surfactants is achieved by the ionic self-assembly (ISA) route. The structure and phase behavior of the complexes were examined by IR spectroscopy, differential scanning calorimetry, optical microscopy, and small- and wide-angle X-ray scattering. This class of materials shows a number of interesting physicochemical properties, namely liquid-crystalline phases (both thermotropic and lyotropic) and strong photoluminescence. The photophysical behavior (fluorescence spectra, fluorescence lifetimes, fluorescence quantum yield) of the complexes differs widely in solid powders, films, and solutions. The amphiphilic cationic surfactants not only play a structural role but also have a strong influence on the photophysical properties of E. The photophysical behavior of E can in this way be easily modified by its organizational motifs.     

The parabolic focal conic texture in a lyotropic liquid-crystalline polymer

Hydroxypropyl cellulose (HPC) forms liquid-crystalline solutions in both water and methanol. When these solutions are sheared, the banded texture seen in many liquid-crystalline polymers is formed. Detailed optical microscopy of the bands has been carried out, showing that the bands arise from a smooth variation in the orientation of the local extinction directions, and not (as previously suggested in the literature) from sharp kinks. Over a period of time, the bands degenerate to form a new texture, which appears as a square grid pattern of extinction when specimens are viewed between crossed polars. The location of the corners of the squares depends on whether the microscope is focused near the top or bottom surface. When focus is altered to the middle of the sample, the periodicity of the pattern is halved. This texture is identified with the parabolic focal conies previously seen in small molecule smectic and cholesteric materials.     

Highly luminescent gels and mesogens based on elaborated borondipyrromethenes

Supramolecular gels and liquid-crystalline materials containing borondipyrromethene (F-Bodipy) are a new class of highly luminescent materials built by attachment of long-chain alkoxydiacylamido scaffoldings to boradiazaindacene templates. Robust gels were formed in nonane, and luminescence spectroscopy was used to probe the aggregation processes of the flat indacene cores. Coincidently, columnar mesophase was obtained from the pure material over a wide temperature range, allowing textural observations by fluorescence microscopy.     

The melt anisotropy of ultrahigh-molecular-weight polyethylene

In the course of melt-flow crystallization studies with ultrahigh-molecular-weight polyethylene (UHMWPE), we observed that the melt of UHMWPE is highly anisotropic above its equilibrium melting point and has a tendency to fibrillate. An examination of the melt anisotropy of UHMWPE by optical, Thermal, and x-ray analysis indicates that the melt anisotropy persists at 345°C, i.e., the temperature at which the polymer degrades under nitrogen, and appears similar to a smectic liquid-crystalline phase.     

High-resolution characterization of liquid-crystalline [60]fullerenes using solid-state nuclear magnetic resonance spectroscopy

Liquid-crystalline materials containing fullerenes are valuable in the development of supramolecular switches and in solar cell technology. In this study, we characterize the liquid-crystalline and dynamic properties of fullerene-containing thermotropic compounds using solid-state natural abundance (13)C NMR experiments under stationary and magic angle spinning sample conditions. Chemical shifts spectra were measured in isotropic, liquid-crystalline nematic and smectic A and crystalline phases using one-dimensional (13)C experiments, while two-dimensional separated local-field experiments were used to measure the (1)H- (13)C dipolar couplings in mesophases. Chemical shift and dipolar coupling parameters were used to characterize the structure and dynamics of the liquid-crystalline dyads. NMR data of fullerene-containing thermotropic liquid crystals are compared to that of basic mesogenic unit and mesomorphic promoter compounds. Our NMR results suggest that the fullerene-ferrocene dyads form highly dynamic liquid-crystalline phases in which molecules rotate fast around the symmetry axis on the characteristic NMR time scale of approximately 10 (-4) s.