Calorimetric studies of poly (2-phenoxyethylacrylate)/5CB mixtures

The thermophysical properties of mixtures of poly (2-phenoxyethylacrylate) and 4-cyano-4'-pentyl-biphenyl, 5CB, are investigated using polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The polymer has a molar mass M w = 181 000 g mol -1 ; the low molecular mass liquid crystal exhibits a nematic to isotropic transition at 35.3°C and crystallizes below 23°C. The phase diagram exhibits miscibility gaps in certain regions of temperature and composition where coexisting nematic and isotropic phases are found. From a practical point of view when considering the electro-optical applications of these systems, it proves to be useful to know precisely the amount of small liquid crystal molecules dissolved in the polymer matrix and the concentration of polymer in the nematic phase. The former quantity has a mechanical impact due to a plasticizing effect, an optical impact since it changes the polymer refractive index, while the polymer in the nematic phase shifts the transition temperatures influencing the electro-optical response of the liquid crystal. The present work addresses these important aspects using POM and DSC.     

Direct observation of the main-chain conformation of a combined liquid-crystal polymer

The conformation of the main-chain (backbone) of a combined main-chain/side-chain liquid crystalline polymer has been qualitatively determined by small angle neutron scattering in the oriented nematic, the smectic A and the smectic C phases. The polymer backbone presents only a weak anisotropy, of prolate shape, in the nematic and the smectic C phases. A stronger reorientation of the backbones in the direction of the applied magnetic field is measured for the S_A phase. However, this anisotropy remains small compared to the stretching of a main-chain liquid crystal polymer and the smectic structure results apparently from side-chain ordering. On the other hand, hydrodynamic measurements show that the combined polymer, in solvent, is as flexible as a polystyrene chain. This result is compatible with an explanation for the weak observed anisotropy.     

Phase biaxiality in nematic liquid crystalline side-chain polymers of various chemical constitutions

In a previous deuterium NMR study conducted on a liquid crystalline (LC) polymer with laterally attached book-shaped molecules as the mesogenic moiety, we have revealed a biaxial nematic phase below the conventional uniaxial nematic phase (Phys. Rev. Lett. 2004, 92, 125501). To elucidate details of its formation, we here report on deuterium NMR experiments that have been conducted on different types of LC side-chain polymers as well as on mixtures with low-molar-mass mesogens. Different parameters that affect the formation of a biaxial nematic phase, such as the geometry of the attachment, the spacer length between the polymer backbone and the mesogenic unit, as well as the polymer dynamics, were investigated. Surprisingly, also polymers with terminally attached mesogens (end-on polymers) are capable of forming biaxial nematic phases if the flexible spacer is short and thus retains a coupling between the polymer backbone and the LC phase. Furthermore, the most important parameter for the formation of a biaxial nematic phase is the dynamics of the polymer backbone, as the addition of a small percentage of low molar mass LC to the biaxial nematic polymer from the original study served to shift both the glass transition and the appearance of detectable biaxiality in a very similar fashion. Plotting different parameters for the investigated systems as a function of T/Tg also reveals the crucial role of the dynamics of the polymer backbone and hence the glass transition.     

Calorimetric studies of poly (2-phenoxyethylacrylate)/5CB mixtures

The thermophysical properties of mixtures of poly (2-phenoxyethylacrylate) and 4-cyano-4′-pentyl-biphenyl, 5CB, are investigated using polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The polymer has a molar mass M _w = 181 000 g mol ^-1 the low molecular mass liquid crystal exhibits a nematic to isotropic transition at 35.3°C and crystallizes below 23°C. The phase diagram exhibits miscibility gaps in certain regions of temperature and composition where coexisting nematic and isotropic phases are found. From a practical point of view when considering the electro-optical applications of these systems, it proves to be useful to know precisely the amount of small liquid crystal molecules dissolved in the polymer matrix and the concentration of polymer in the nematic phase. The former quantity has a mechanical impact due to a plasticizing effect, an optical impact since it changes the polymer refractive index, while the polymer in the nematic phase shifts the transition temperatures influencing the electro-optical response of the liquid crystal. The present work addresses these important aspects using POM and DSC.     

Phase equilibria and phase separation dynamics in a polymer composite containing a main-chain liquid crystalline polymer

Various topological phase diagrams of blends of main-chain liquid crystalline polymer (MCLCP) and flexible polymer have been established theoretically in the framework of Matsuyama–Kato theory by combining Flory–Huggins (FH) free energy for isotropic mixing, Maier–Saupe (MS) free energy for nematic ordering in the constituent MCLCP, and free energy pertaining to polymer chain-rigidity. As a scouting study, various phase diagrams of binary flexible polymer blends have been solved self-consistently that reveal a combined lower critical solution temperature (LCST) and upper critical solution temperature (UCST), including an hourglass phase diagram. The calculated phase diagrams exhibit liquidus and solidus lines along with a nematic–isotropic (NI) transition of the constituent MCLCP. Depending on the strengths of the FH interaction parameters and the anisotropic (nematic–nematic) interaction parameters, the self-consistent solution reveals an hourglass type phase diagram overlapping with the NI transition of the constituent MCLCP. Subsequently, thermodynamic parameters estimated from the phase diagrams hitherto established have been employed in the numerical computation to elucidate phase separation dynamics and morphology evolution accompanying thermal-quench induced phase separation of the MCLCP/polymer mixture. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3621-3630, 2006     

有机光导液晶光阀(透射式)及其性能的研究

本文报道用聚乙烯咔唑-2,4,7三硝基芴酮电荷转移复合物作光导层,与向列型及胆甾向列型混合液晶组成的夹心池结构制成的扭曲场效应、相变存储效应及动态存储效应三种直流透射式光阀及其性能的研究结果。制得的光阀均有明显开关效应。此外,还详细研究了扭曲场效应液晶光阀的阈值电压、对比度及上升时间与写入光功率的依赖关系。用白光写入,He-Ne激光读出,在扭曲场效应光阀上可实现非相干光-相干光转换,得到图象。用MTF法测得的光阀分辨率为34lps/mm。     

含联苯结构侧链液晶聚合物的合成及相行为的研究

液晶聚合物从结构上可分为3种:侧链型、主链型和主侧链型。侧链型液晶聚合物主要是聚丙烯酸酯类、聚硅氧烷类以及磷腈聚合物类。Gray等对聚丙烯酸酯类含不同取代基的联苯结构液晶聚合物进行了研究,结果表明无间隔基且取代基为氰基和饱和脂肪基时,该聚合物呈现近晶型液晶行为。为了增加介晶单元的长径比及刚性,本文在聚甲基丙烯酸酯侧链     

Numerical analysis for a nematic droplet in polymer dispersed liquid crystals

Starting from the Landau-de Gennes free energy expression, the author has numerically analysed the director pattern in a nematic droplet of polymer dispersed liquid crystals. The nematic director has been understood as the eigenvector, which corresponds to the largest eigenvalue of the tensor order parameter. To investigate the droplet structure influence, all equations have been treated on the curvilinear coordinate system which is generated along the droplet boundary. In the case of spherical and spheroidal droplets with normal strong anchoring, the director exhibits an axial configuration and a disclination ring. The ring radius and the capactiance of the system change without hysteresis with the applied voltage.     

Non-equilibrium thermal behaviour of a main chain thermotropic polymer

The effect of thermal treatment on the thermodynamic properties and structure of a nematic thermotropic main chain polymer with mesogenic groups containing 3,3'-biphenylene units and octamethylene flexible spacers (BF8) has been studied by DSC and X-ray scattering. We have found that BF8 samples do not crystallize even on very slow cooling from the isotropic state, and possessed a glassy nematic structure at room temperature. The strong influence of the cooling rate on both the enthalpy of the nematic-isotropic transition and the rise of specific heat at the glass transition for BF8 samples was observed. It was attempted to explain this result in terms of the improvement of the nematic structure during cooling.     

Optical properties of stretched polymer dispersed liquid crystal films

The basic mechanisms determining the formation of optical anisotropy in stretched, thin polymer dispersed liquid crystal (PDLC) films with micron sized nematic droplets have been studied experimentally and the results analysed in terms of a proposed theoretical model. The experiments were performed on PDLC films with the bipolar nematic director configuration in the droplets, where the film transmittance, microscopic structure, and birefringence of the polymer matrix were studied. It is shown that the orientational ordering of bipolar nematic droplets, introducing the main contribution to the ability of stretched PDLC film to polarize the transmitted light, is strongly dependent upon initial droplet shape and the elastic properties of the polymer matrix. The 'anomalous' nematic director orientation is also observed in a portion of elongated droplets where the axes of bipolar configurations do not coincide with the major axes of the droplet cavities due to the presence of inclusions at the cavity walls. The effect of alternation of droplet size and shape upon stretching and the influence of optical anisotropy of the polymer matrix on film transmittance are analysed. On the basis of the results obtained, simple criteria for optimization of main PDLC polarizer performance are formulated.     

Synthesis and properties of poly(1,2–8,9-trans-quinacridono)

The aromatic ladder polymer, poly(1,2–8,9-trans-quinacridono) (PQ) has been synthesized. The intermediate polymer was also characterized. Electron paramagnetic resonance (EPR) and conductivity measurements were made on PQ. PQ packs in nematic liquid crystal form. Iodine intercalates and destroys the order during doping, while raising its conductivity by five orders of magnitude.     

Rheology of a thermotropic polyester in the nematic and isotropic states

The rheological properties of a thermotropic polyester were determined in the nematic and isotropic states. In the isotropic state, the viscosity is almost constant and the polymer is only slightly elastic. The nematic phase has a lower viscosity than the isotropic, except at low frequencies or shear rates, where the viscosity increases as though the polymer had a yield stress. There is a marked dependence of the rheology on shear history. The effects of shearing can be erased by returning the material first to the isotropic state and then back to the nematic state. The results are discussed with reference to analogous observations in small-molecule liquid crystals and in thermotropic aromatic co-polyesters.     

Nature of the liquid-crystalline phase in supramolecular linear polymers

The development of the liquid crystal (LC) state in the melt of a supramolecular linear LC polymer based on a diacid and bipyridine base has been studied by IR spectroscopy and polarizing optical microscopy. Relying on experiments on the hydrogen-bonded complex formation and statistical analysis of the formation kinetics of the nematic phase, it is inferred that the system under study behaves like a binary mixture of weakly interacting components rather than a polydisperse polymer.     

Theoretical simulation of thermally induced phase separation in a main‐chain liquid‐crystalline polymer solution

Phase diagrams of main‐chain liquid‐crystalline polymer (MCLCP) solutions have been calculated self‐consistently on the basis of a simple addition of the Flory–Huggins free energy for isotropic mixing, the Maier–Saupe free energy for nematic ordering, and the Flory free energy for chain rigidity of the MCLCP backbone. The calculated phase diagram is an upper critical solution type overlapping with the nematic–isotropic transition. The phase diagram consists of liquid–liquid, liquid–nematic, and pure nematic regions. Subsequently, the dynamics of thermally induced phase separation and morphology development have been investigated by the incorporation of the combined free energy density into the coupled time‐dependent Ginzburg–Landau (model C) equations, which involve conserved compositional and nonconserved orientational order parameters. The numerical calculations reveal a variety of the morphological patterns arising from the competition between liquid–liquid phase separation and nematic ordering of the liquid‐crystalline polymer. Of particular interest is the observation of an inflection in the growth dynamic curve, which may be attributed to the nematic ordering of the MCLCP component, which leads to the breakdown of the interconnected domains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 913–926, 2003     

Phase equilibria of polymer dispersed liquid crystal systems in the presence of an external electrical field

The effect of an external electrical field on phase behaviors is reported for polymer dispersed liquid crystal films of 4′‐pentyl‐4‐biphenylcarbonitrile/poly(methyl methacrylate) binary mixtures with various polymer molecular weights. The experimental results show that increasing the molecular weight of the polymer or the electrical field intensity can give rise to an increase in the phase‐transition temperature and a widening of the binary phase region. The lattice theory, regarding a binary system consisting of a rigid nematic liquid crystal and a random polymer, has been extended to the case in which an external electrical field is present. A comparison of the theoretical predictions with the experimental results has been carried out, and satisfactory agreement has been found. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1898–1906, 2007     

Non-equilibrium thermal behaviour of a main chain thermotropic polymer

Abstract

The effect of thermal treatment on the thermodynamic properties and structure of a nematic thermotropic main chain polymer with mesogenic groups containing 3,3′-biphenylene units and octamethylene flexible spacers (BF8) has been studied by DSC and X-ray scattering. We have found that BF8 samples do not crystallize even on very slow cooling from the isotropic state, and possessed a glassy nematic structure at room temperature. The strong influence of the cooling rate on both the enthalpy of the nematic-isotropic transition and the rise of specific heat at the glass transition for BF8 samples was observed. It was attempted to explain this result in terms of the improvement of the nematic structure during cooling.     

一种侧链液晶高分子的合成与表征

合成了一种主链为甲基丙烯酸酯 ,侧链是三个苯环以酯键相连的介晶基元 ,柔性间隔段为两个亚甲基的新的侧链液晶高分子 .聚合物和单体的化学结构、液晶相转变和液晶态织构采用红外光谱、核磁共振、偏光显微镜、差热分析和广角X光衍射进行了表征 .研究表明 ,单体呈现近晶相和向列相两个液晶相 ,聚合物在很宽的温度范围内呈向列相 .该单体和聚合物在一定条件下可形成固化诱导条带织构     

Induction of the cholesteric mesophase in hydrogen-bonded blends of polymers with a low molecular mass chiral dopant

A family of new hydrogen bonded complexes based on comb-shaped LC copolymers containing alkyloxy-4-oxybenzoic acid mesogenic fragments and chiral dopant molecules, derivatives of pyridine-4-carboxylic acid has been prepared. At concentrations of chiral groups in the range 1-25 mol%, induction of the cholesteric phase is observed. The temperature dependences of the selective light reflection wavelength were studied, and the helix twisting power was calculated. Depending on the type of polymer nematic matrix, this value varies in the range 12.1 to 18.3mum 1. With respect to optical properties, the chiral nematic phase in the hydrogen-bonded complexes is comparable to that in classical cholesteric copolymers in which the chiral group is covalently bound to the polymer chain.