Effect of swelling on the cholesteric structure of ethyl‐cyanoethyl cellulose/crosslinked poly(acrylic acid) composite films

The swelling behavior of ethyl‐cyanoethyl cellulose [(E‐CE)C]/crosslinked poly(acrylic acid) [PAA] cholesteric liquid crystalline composite films and the structural variation of the cholesteric phase during the swelling and the drying process were studied. It was found that the wavelength of the selective reflection of the composite films was shifted to the long wavelength direction during swelling. Both the pitch of the cholesteric phase and the distance between neighboring molecular layers were increased, and the helix axis was inclined after swelling. Moreover, the swelling behavior of the composite films in water was reversible, which means that the optical properties and structural characters of the films could be changed back to their original states after the films were dried from the equilibrium swelling state. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3574–3578, 2004     

丙烯酸铅对乙基纤维素胆甾型液晶的影响

本文利用紫外-可见分光光度计研究了丙烯酸铅(PbA)对乙基纤维素(EC)/丙烯酸(AA)胆甾型液晶的影响,研究发现:在EC/AA胆甾型液晶中,其最大选择性反射波长和螺距随溶液浓度增加而降低;PbA的加入也使反射波长和螺距降低,并且溶液中PbA浓度越大,反射波长和螺距降低越多,这可能是由于Pb2+与纤维素分子的络合作用,拉近了相邻EC分子链距离,导致胆甾型液晶溶液中的层间分子距离减小所致。利用这种性质调节纤维素胆甾型液晶的光学反射性能。     

α-氰基二苯乙烯类液晶研究进展

分类综述了α-氰基二苯乙烯类液晶的研究进展,包括氰基二苯乙烯棒状液晶、氰基二苯乙烯弓形液晶及氰基二苯乙烯多链形液晶,盘状液晶等。介绍了他们自组装成的多种液晶相及光电性质,以及对光、电、磁、压力等多种环境因素快速的响应性质。氰基二苯乙烯类液晶作为一种新型的荧光液晶材料,具有压敏效应、聚集发光效应及离子识别效应等,已成为当前人们重点研发的功能材料。     

A study of photooptical processes in photosensitive cholesteric azobenzene-containing polymer mixture under an action of the polarized and nonpolarized light

New liquid crystalline cholesteric mixture consisting of azobenzene-containing side-chain copolymer and the chiral low-molar-mass dopant (5%) was prepared and its properties were studied. It was shown that freshly prepared spin-coated thin films are optically isotropic. However, the films possess a noticeable circular dichroism with a maxima corresponding to the absorbance of the nonchiral azobenzene fragments. This phenomenon is an evidence for the existence of the helical supramolecular structure elements in the mixture films. An annealing of the films at temperatures above the glass transition leads to the strong increase in the circular dichroism due to formation of the perfect cholesteric phase. UV light irradiation results in the E-Z isomerization of azobenzene groups and the significant drop in circular dichroism values (almost to zero) both for the fresh and the annealed films that is associated with the transition from cholesteric to the fully isotropic state. An action of polarized UV and visible light leads to the photoorientation of azobenzene groups perpendicular to the electric vector of the polarized light. Kinetic features of the photoorientation processes in cholesteric phase in comparison with nematic systems were studied. It has been experimentally found that the helical order to some extent prevents the photoorientation of the side groups. Upon UV irradiation of the thick, planarly-oriented films of the mixture at temperatures higher than glass transition, the selective light reflection maximum is shifted to the long-wavelength spectral region. All photoinduced phenomena occurring in the mixture are thermally reversible and annealing of the films at temperatures above glass transition results in the back recovery to the cholesteric nonoriented state and to the initial helix pitch value.     

Chiroptical filters from aqueous (hydroxypropyl) cellulose liquid crystals

An experimental procedure has been designed for the preparation of aqueous mesophases of (hydroxypropyl)cellulose (HPC) exhibiting a stable low turbidity Sandwich chiroptical filters have been made from these right-handed cholesteric liquid crystals confined between two parallel glass plates. Their optical properties, studied with new circular polarizers prepared from oriented polyethylene films, depend on the mesophase thickness. Thin filters (liquid crystal thickness ≤ 200 μm) reflect selectively up to 36% of normal incident light (i.e., 72% of the right-handed circularly polarized component) in a very narrow wavelength band (bandwidth ≤ 10 nm). An increase of the reflected intensity is observed at higher sample thickness, although it is accompanied by an increasing loss of selectivity of the filter toward circularly polarized light. However, a range of thickness exists where both selectivity and reflectivity are close to their optimum values. The availability, low cost, and UV resistance of (hydroxypropyl)cellulose make HPC–water liquid crystals attractive for optical applications.     

Preparation and mechanical properties of chemically cross-linked hydroxypropyl cellulose solid films retaining cholesteric liquid crystalline order

Hydroxypropyl cellulose films were cast from liquid crystalline solutions with a crosslinking agent. The solubility test and the optical measurements of the resultant films were performed. The tensile, dynamic mechanical, and creep properties of the films were determined. The data of solubility in water determined that the cast films are cross-linked, and the data of circular dichroism spectra, that the cast films retain the cholesteric liquid crystalline order (right-handed sense). Both findings clarified that the cast films retain the cholesteric order fixed by cross-linking. The cross-linking depended on the pairs of the solvent–cross-linking agent. The mechanical properties also depended on the pairs: the tensile strength and moduli did not always increase with cross-linking. The creep resistance improved with cross-linking. The thermally activated Eyring process could be applied and the activated volumes were evaluated for water- and methanol-cast films. There were not clear phenomenological correlations between the mechanical properties of our films.     

Influence of polymerization on the cholesteric structure in ethyl-cyanoethyl cellulose/acrylic acid solutions

Ethyl-cyanoethyl cellulose ((E-CE)C) forms cholesteric liquid crystals in acrylic acid (AA) and the cholesteric order in the solutions can be frozen when the AA is quickly polymerized but the cholesteric structure is changed after the polymerization though the property of the selective reflection is reserved. The maximum wavelength of the selective reflection of the cholesteric phase λ_max is shifted to the shorter wavelength direction and the selectivity and the intensity of the reflection are decreased after the AA polymerization. It is found that the shift of the reflection wavelength results from the decrease of the cholesteric pitch after the polymerization and the variation of the cholesteric pitch is decreased with increasing the (E-CE)C concentration. The decrease of the pitch after the AA polymerization is due to the volume shrinkage of the solvent monomer during the polymerization and it depends on the polymerization temperature.     

分子结构对乙基氰乙基纤维素/丙烯酸胆甾型液晶性的影响

乙基氰乙基纤维素 [(E -CE)C]可溶于丙烯酸 (AA)形成胆甾型溶致液晶体系 ,液晶溶液的临界浓度 (C1 )与 (E -CE)C的分子量 (MW)有关 ,MW 越高 ,C1 越低。同时 ,C1 还受 (E -CE)C氰乙基取代度 (DS)的影响 ,DS越大 ,C1 越低。相同DS时 ,胆甾相的螺距 (P)随MW 增加而增大 ;在MW 相近时 ,随DS的升高 ,P先减小 ,后增大 ,在DS 0 .2～ 0 .3之间有最小值。P随 (E -CE)C/AA溶液浓度的增大而降低。 (E -CE)C/AA溶液中的AA快速聚合后 ,体系胆甾相选择性反射光的能力和选择性均有所降低 ,并且最大选择性反射光的波长 (λmax)蓝移。聚合前溶液的浓度越小 ,聚合后λmax的变化值越小     

Optical properties of ethyl‐cyanoethyl cellulose/poly(acrylic acid) cholesteric liquid crystalline composite films

Ethyl‐cyanoethyl cellulose [(E–CE)C]/poly(acrylic acid) (PAA) composite films were prepared by photopolymerizing acrylic acid (AA) in (E–CE)C/AA cholesteric liquid crystalline solutions. With the selection of suitable concentrations, (E–CE)C/PAA composite films showed vivid colors due to the selective reflection property of the cholesteric phase. It was found that the wavelength of reflection was a function of the concentration of (E‐CE)C, and the reflectivity was increased with increasing thickness of the film. The selective reflection of the composite holds well upon heating at temperatures below 160°C. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 213–217, 2004     

光聚合对乙基氰乙基纤维素/丙烯酸胆甾相结构的影响

乙基氰乙基纤维素 [(E -CE)C]能够很好地溶解在丙烯酸 (AA)中并形成胆甾型液晶溶液。在 (E -CE)C/AA溶液中加入适当的光引发剂 ,采用紫外光引发聚合抑制聚合过程中相分离的发生 ,可以制得保持胆甾相结构的复合物。聚合反应会对胆甾相的结构产生一定的影响。文章研究了溶液浓度、聚合温度和 (E -CE)C分子量等因素对聚合以后胆甾相选择反射光波长及结构的影响。     

Cholesteric order in aqueous solutions of the polysaccharide Xanthan

Summary Measurements of birefringence, optical rotation and laser light diffraction show that aqueous solutions of the polyelectrolytic polysaccharide Xanthan at a concentration of 7.5 % (vol/vol) have long range order very similar to cholesteric liquid crystals. The cholesteric screw is left handed implying a rod-like conformation and right handed helicity of individual molecules. The cholesteric phase separates from a less concentrated isotropic solution and spherolites are formed.     

Crosslinked hydroxypropyl cellulose films retaining cholesteric liquid crystalline order. I. Effects of cast conditions and heat treatment on the textures and order of films

To eliminate the shear-induced band texture and wrinkled texture observed on the free surface of cellulosic solid cast films retaining cholesteric liquid crystalline order, we proposed a storing process of the cast solutions: the solution is stored in the same solvent vapor atmosphere as the solution. The effect of cast conditions (the storing time) on those textures and the cholesteric liquid crystalline order was determined using the lyotropic liquid crystalline solution of hydroxypropyl cellulose in methanol with crosslinker. Furthermore, the effect of heat treatment on the liquid crystalline order in the cast films was determined. The resultant crosslinked films were observed with a polarized microscope and a scanning electron microscope, and were investigated with circular dichroism. Our findings showed that the proposed storing process is needed before starting the cast process. During the process the textures vanished, due to the relaxation of the residual stress in the solution, the cholesteric liquid crystalline order became stable, and the cholesteric pitch decreased with increasing storing time. The heat treatment also affected the liquid crystalline order of the films; the peak in the circular dichroism spectrum sharpened and shifted with heat treatment, and the shift in peak seemed to depend on the crosslinker concentration. Furthermore, the crosslinking proceeded with heat treatment. © 1995 John Wiley & Sons, Inc.     

Thermotropic cholesteric mesophases in copoly(γ-n-alkyl l-glutamate)s

Summary Thermotropic cholesteric mesophases were found for three types of -helical copoly(-n-alkyl L-glutamate)s; the combination of the n-alkyl groups was methyl-hexyl, methyl-octyl, and propyl-octyl. Cholesteric colors due to the selective reflection were observed in the temperature range from 110 to 190°C for the films with copolymer compositions of about 50/50 in mol%. These thermotropically mesomorphic copolymers had disordered structures in the molecular packing as inferred from the x-ray diffraction patterns. The cholesteric sense was right-handed, since the negative circular dichroism associated with the cholesteric pitch was observed for all the mesomorphic films. The temperature dependence of the pitch was discussed in comparison with that of lyotropic liquid crystals of these polymers.     

Fine structure in cholesteric fingerprint texture observed by scanning electron microscopy

Summary The fine structure in some cholesteric fingerprint textures of cyanoethyl chitosan (CNCS)/acrylic acid solution and photo-solidified CNCS/polyacrylic acid composite film was studied using scanning electron microscopy (SEM), small angle light scattering (SALS) and polarizing optical microscopy (POM). Permanganic etching was developed to reveal the cholesteric liquid crystalline textures in the composite films. A schematic model was presented to explain this kind of fine structure. The directors within each cholesteric molecular layer did not orient in nematic-like order, but varied their orientation by an ill-defined period. Received: 4 October 1999/Revised version: 13 December 1999/Accepted: 24 December 1999     

Controlling the Phase Behavior and Reflection of Main-Chain Cholesteric Oligomers Using a Smectic Monomer

Cholesteric liquid crystals (CLCs) are a significant class of temperature-responsive photonic materials that have the ability to selectively reflect light of a specific wavelength. However, the fabrication of main-chain CLC oligomers with dramatic reflection band variation upon varying the temperatures remains a challenge. Here, a feasible method for improving and controlling the responsiveness of main-chain cholesteric liquid crystal oligomers by the incorporation of a smectic monomer is reported. The smectic monomer strengthens the smectic character of the oligomers and enhances the magnitude of the change of the pitch as a function of temperature upon approaching the cholesteric–smectic phase transition temperature. The central wavelength of the reflection band can be easily modified by mixing in an additional chiral dopant. This promising method will open the door to the preparation of temperature-responsive photonic devices with excellent responsiveness.     

Synthesis and characterization of novel monomers and polymers containing chiral (−)-menthyl groups

To investigate the steric effects of chiral menthyl groups on the induction of cholesteric liquid crystals and the sensitivity of the photoisomerizable azobenzene derivatives, a series of chiral monomers and a photoisomerizable chiral azobenzene derivative with various spacers end-capped with (−)-menthyl group were synthesized. The structures of the novel chiral compounds synthesized in this investigation were identified using ¹³C NMR, FTIR, and elemental analysis. The phase transition temperatures of the chiral compounds were investigated using X-ray diffraction, differential scanning calorimetry, and polarizing optical microscopy. The thermogravimetric characteristics, the glass-transition temperatures (T_g) and the weight-average molecular weights (M_w) of the homopolymers were also evaluated. Polymers containing chiral menthyl groups with a biphenyl segment were found to reveal high thermal resistance. However, the existence of the steric hindered menthyl group disturbed the arrangement of chiral monomers leading to the disappearance of liquid crystal phases. The specific optical rotation of the synthesized monomers and polymers were also evaluated. The effect of the synthesized chiral compounds, monomers and photoisomerizable azobenzene derivative on the induction of the cholesteric liquid crystal films was investigated. The morphological network structure of the polymer matrix inside a liquid crystal cell was studied using a scanning electron microscope (SEM). The phototuning ability of the AzoM on the cholesteric liquid crystals was also established.     

Synthesis,structures, and properties of side‐chain cholesteric liquid‐crystalline polysiloxanes

The synthesis of three cholesteric monomers and side‐chain liquid‐crystalline polymers was described. The structure–property relationships of monomers IM–IIIM and polymers IP–IIIP were discussed. Their phase behavior and optical properties were investigated by differential scanning calorimetry, thermogravimetric analyses (TGA), and polarizing optical microscopy. Monomers IM–IIIM exhibited cholesteric oily‐streak texture and focal‐conic texture. Polymers IIP and IIIP revealed smectic A fan‐shaped texture and cholesteric grandjean texture, respectively. Experimental results demonstrated that the selective reflection of IM–IIIM shifted to the short‐wavelength region with increasing the flexible spacer length or decreasing the rigidity of the mesogen. Polymers with a longer flexible spacer had lower glass‐transition temperatures and wider mesomorphic temperature ranges. TGA showed that the temperatures at which 5% weight loss occurred were greater than 300°C for all the polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3944–3950, 2003     

Study on the Optical and Mesomorphic Properties of Cholesteric Side-Chain Liquid Crystalline Elastomers Containing a Nematic Cross-Linking Agent

To study the effect of the content of the nematic cross-linking units on the mesophase behaviors, the optical and mesomorphic properties of liquid crystalline elastomers (LCEs), aseries of LCEs have been synthesized by hydrosilylation reaction with poly(methylhydrogeno)siloxane, a cholesteric liquid crystalline monomer, and a nematic cross-linking agent. The chemical structures and properties of the synthesized LCEs have been investigated by use of various techniques. Homopolymer P₀ bearing only cholesteric component displays a smectic A phase, but elastomers P₁-P₅ containing different content of nematic cross-linking units show a cholesteric mesophase. The reflection wavelengths of theLCEs show a weak temperature dependence at lower temperatures but a strong temperature dependence at higher temperatures. Furthermore, the maximum reflection wavelengths of the LCEs can be stabilized over a wide temperature range when the LCEs are heated, suggesting that the helical structure and pitch of the cholesteric phase can be stabilized with a polymer network.     

Studying cubic boron nitride by Raman and infrared spectroscopies

In this paper, optical properties of cubic boron nitride (cBN) in forms of films, powders and monocrystals are studied in vibrational spectral regions. For cBN single crystals, the reststrahlen peak reflectivity of about 95% has been obtained. The second-order Raman scattering spectra induced by visible light excitation is also presented. The infrared two-phonon absorption bands are suggested as additional fingerprints for identification of the cBN nature.     

Chiral polymer networks with a broad reflection band achieved with varying temperature

In this study, we demonstrate a novel method for fabricating a single layer cholesteric liquid crystal (CLC) film with non-uniform pitch distribution by utilizing the chiral polynetworks. A chiral monomer, the helical twist power (HTP) of which decreases with the increase of temperature, was synthesized. The temperature dependence of the pitch of the mixtures before and after polymerization was investigated. To broaden the reflection band, the experimental processes of thermally induced pitch variation were presented. The results suggest that the chirality of the polymer network plays an integral role in the reflection spectra. Additionally, scanning electron microscopy (SEM) was used to examine the role of the polymer network induced by polymerization temperature. These wide-band reflection optical properties make the CLC gels interesting for their potential applications in many fields, such as colour filters, brightness enhancement films, smart switchable reflective windows etc.