ECEC/AA液晶溶液取向态织构及其自由基聚合

利用光学显微镜和小角光散射等方法研究了乙基氰乙基纤维素(ECEC)/丙烯酸(AA)取向液晶态织构。在切应力作用下ECEC/AA液晶溶液形成带状结构,其中大分子链沿切应力方向呈锯齿形取向,溶液浓度越高,取向液晶溶液中大分子链有序性越高,带状织构中的条带愈窄。通过紫外光引发聚合方式获得了保持取向液晶态中带状织构的复合物膜。     

氰乙基纤维素/二甲基乙酰胺液晶溶液的研究

本文利用Abbe折射仪,热台偏光显微镜,小角光散射等方法研究了氰乙基纤维素/二甲基乙酰胺液晶溶液的形成,形态结构和某些性质。溶液随浓度的增加,从各向同性态经过两相共存状态,转变成为单一的液晶态。该液晶是胆甾型的。溶液的双折射Δn随浓度的增加或温度的降低而增大。在无外力作用时,液晶相由许多无规分布的取向微区组成。液晶溶液受切应力后形成“条纹结构”,大分子链沿切应力方向取向,并在各条纹中排列有序。     

甲基氰乙基纤维素溶致性液晶的研究

甲基氰乙基纤维素在二氯乙酸(DOA)中能形成溶致性液晶。本文利用FTIR仪、阿贝折射仪以及偏光显微镜等手段,研究了该液晶溶液相转变过程中分子间的相互作用,折光行为,以及液晶相织构等的变化。发现相转变时分子间的相互作用发生大的变化。液晶相由许多小的取向区域组成,各小取向区域的取向程度和方向不同,随着浓度的提高,液晶内的有序程度逐渐提高,各小取向区域的取向方向逐渐趋于一致,总的取向度随之升高。     

氰乙基纤维素/二甲基乙酰胺液晶溶液的取向态织构

本文用偏光显微镜、小角光散射和消偏振光法对受切应力后取向的氰乙基纤维素/二甲基乙酰胺液晶溶液的织态结构进行了研究。证明在取向的液晶溶液中,分子链沿切应力方向高度取向。相邻条纹间的分子链取向稍有不同。     

氰乙基纤维素/二甲基乙酰胺液晶溶液的研究

本文利用 Abbe'折射仪和热台偏光显微镜研究了氰乙基纤维素/二甲基乙酰胺液晶溶液的形成、结构和某些性质。它与许多溶致性液晶一样,随溶液浓度的增加,溶液从各向同性状态经过两相共存状态转变成为单一的液晶态。溶液的双折射△n 随浓度增加而增加,随温度的升高而降低。升温速率的改变对测定临界温度值有一定的影响。液晶相在无外力作用时由许多取向的、无规分布的微区域组成。受到切应力后,微区变成长条状。分子链沿切应力方向取向,并在垂直于切应力方向上在各微区域内排列有序,相邻两微区的分子链的取向方向稍有不同。     

乙基醋酸纤维素液晶相织构的温度依赖性

本文利用热台偏光显微镜观察了在不同温度下乙基醋酸纤维素/二氯乙酸液晶溶液中液晶相的双折射纹理织构的变化。证明液晶相中分子链排列的有序程度不是完全相同的。在一定的升温速率下加热溶液,有序程度较低的部份首先被破坏。升温速率足够慢时,较高温度虽然使液晶聚集体缩小,但在液晶相内,分子键排列的有序程度不会降低,有时甚至还会增加。从各向同性溶液转变为液晶溶液时,液晶相首先形成圆盘织构。在两相共存的溶液中,分散相都尽可能以圆形存在于连续相中,以降低体系能量。     

乙基醋酸纤维素液晶态条带织构的形成机理

本文应用平行板移动式和转动式二种剪切装置研究了乙基醋酸纤维素的二氯乙酸体系液晶态受剪过程形成条带织构的临界剪切速率,条带织构的形成机理以及所形成的条带织构在升降温过程中的变化。结果表明,高分子液晶态受剪过程条带织构不是在受剪时产生,而是在受剪停止后的弛豫过程中形成的。可以观察到条带织构出现的诱导时间(t_b),其值的大小与溶液的浓度、剪切速率等因素有关。最后提出一模型来解释高分子液晶态受剪切过程条带织构的形成机理。     

乙基醋酸纤维素液晶相的织态结构观察

乙基醋酸纤维素/二氯乙酸胆甾型液晶溶液的液晶相和各向同性相在两相共存时,表现出明显的相分离行为。在胆甾相中,液晶相的织态结构随浓度而变化,可以形成园盘结构、油纹结构以及取向微区的无规堆集结构。在前两种结构中,分子链排列层垂直于玻片表面,螺旋结构的轴向与玻片表面平行。     

乙基氰乙基纤维素/二氯乙酸溶液的红外光谱研究

本文利用付里叶变换红外光谱法(FTIR)研究了乙基氰乙基纤维素/二氯乙酸溶液的红外吸收谱带随浓度变化的情况。发现某些谱带的位移与溶液的结构有关。特别是溶液中各种氢键的形成或被破坏,对谱带的位移有很大的影响。在液晶相内,呈头—尾相连状态的溶剂分子增多。溶液在临界浓度C_2~*以上还存在一个临界值。在浓度超过该临界值后,溶液的结构呈现出一种比较恒定的状态,各基团的红外吸收谱带基本上不再随浓度的增加而位移。     

乙基氰乙基纤维素／聚丙烯酸复合物及大分子胆甾型液晶相的形态结构特征

对乙基氰乙基纤维素／丙烯酸胆甾型液晶溶液的液晶性，液晶态的织构特征，丙烯酸在液晶溶液中的聚合反应及在反应过程中胆甾型液晶相结构和性能的变化等方面进行了研究，     

BAND-LIKE TEXTURE OF ETHYLCYANOETHYL CELLULOSE MESOPHASE

In the ethyl-cyanoethylcellulose ((E-CE)C)/dichloroacetic acid (DCA) cholesteric liquid crystalline solution, the hand-like texture is formed when the mesophase aggregates with the disk-like texture grow to big enough and merge with each other with increasing concentration. The band-like texture is composed of parallel equidistant bright and dark alternative strips which are about 0.2-2.0 μm in width. In the band-like texture, the layers of ordered polymer chains are perpendicular to the solution film and the axes of helicoids are parallel to it. The width of the strips is different in different zones. Under the effect of an external magnetic field, the strips in the band-like texture first become wider and then narrower gradually.Moreover, the axes of helicoids in the (E-CE) C/DCA mesomorphic solution change from the direction normal to the magnetic field to the agreement with the magnetic field direction.     

Textures and defects in lyotropic liquid crystals of ethyl-cyanoethyl cellulose

Textures and defects in ethyl-cyanoethyl cellulose [(E-CE)C]/dichloroacetic acid (DCA) cholesteric liquid crystalline solutions and in (E-CE)C/polyacrylic acid (PAA) composites were observed and studied by polarizing microscopy and electron microscopy. The existence of χ, λ and τ disclinations were observed in the mesophase with disk-like and band-like textures. Pairs of disclinations with different signs were also found in the mesophase with the band-like texture. Domain walls were observed in (E-CE)C/PAA composite films with cholesteric order by TEM. The orientation of polymer chains in the vicinity of the core of the disclinations is discussed.     

Relaxation Processes in sheared films of ethyl-cyanoethyl cellulose cholesteric liquid crystalline solutions

The relaxation processes in sheared films of ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid (AA) cholesteric liquid crystalline (LC) solutions were studied by polarizing optical microscopy (POM) and UV-Vis spectrophotometry. Under shearing normal to the helix axis and above the critical shear rate, the planar texture arrangement of the (E-CE)C/AA cholesteric LC solution was destroyed and transformed to the nematic phase. Observed by POM, the banded texture formed quickly following the cessation of the shear, but it was unstable and disappeared after several minutes. The reflection spectrum of the sheared (E-CE)C/AA cholesteric LC solution film was recorded as a function of relaxation time. It was found that the selective reflection property was lost under the shear, but the shape of the reflection spectrum recovered quickly with cessation of the shear, and the reflection peak in the spectrum became sharper with time, returning to the original form before shearing. A proposed model of the structural transformation during the relaxation was confirmed by additional optical measurement and transmission electron microscopy.     

MORPHOLOGICAL STUDY ON THE ORIENTED CHITOSAN FILM OBTAINED FROM PRE-SHEARED LIQUID CRYSTALLINE SOLUTION IN DICHLOROACETIC ACID

The oriented chitosan films obtained from pre-sheared liquid crystalline chitosan/dichloroacetic acid (DCA)solutions were studied by means of polarized optical microscopy (POM), scanning electron microscopy (SEM), infra-reddichroism technique and wide angle X-ray diffraction (WAXD). The shear induced band texture in the film was found tocorrespond to the sinusoidal fibrillar microstructure along the shearing direction on the basis of POM and SEM observations.The sinusoidal fibril was found to be lying within the film plane. The model of chitosan molecular orientation in the pre-sheared film with band texture can be established assuming that the main chain orients in the shearing direction and the sidegroup is perpendicular to the shearing direction. The WAXD azimuthal scanning at 2θ= 20° indicates that the (002) planeorients perpendicular to the shearing direction.     

Shear-induced band texture of side group liquid crystalline polymers

The shear-induced band texture of conventional end-on fixed side group liquid crystalline polymers (LCPs) has been investigated by using polarizing optical microscopy (POM), small angle light scattering (SALS) and infra-red dichroism techniques. The band spacing is about 1 μm, which increases very slightly on increasing the temperature of shearing and is independent of shearing rate within the range studied. The band texture is not seen to exhibit an interchange of dark and bright bands on rotation of the sample with respect to the polarizer/analyser, but a typical periodical structure is reflected by the SALS patterns of the band texture. The relaxation behaviour of the bands indicates that the band texture formed here is the result of the orderly aligning of domains exhibiting the focal-conic texture, and this is totally different from the case of main chain LCPs where the band texture is substantially an optical effect of the periodic zigzag or sinusoidal structure of parallel aligned microfibrils. Infra-red dichroism and rotating parallel-plate shearing measurements show that the axes of the backbone of the polymer tend to orient in the shearing direction and the end-on fixed mesogenic side groups tend to align perpendicular to the shearing direction.     

乙基氰乙基纤维素/聚丙烯酸复合物的形态结构

乙基氰乙基纤维素(ECEC)溶于丙烯酸(AA)在浓度足够高时形成胆甾型液品,并在一定的浓度范围内呈现胆甾型液晶特有的选择反射一定波长可见光的特性。自由基引发AA聚合得到ECEC/聚丙烯酸(PAA)复合物。复合物的形态结构与聚合前的溶液状态有关。在从各向同性溶液聚合得到的复合物中,ECEC以无定形棒状聚集态存在;而从各向异性溶液聚合得引的复合物部分保留了聚合前的液晶结构,其中ECEG分子取向排列形成ECEC片层状相区,并在更高层次上ECEC片层与PAA片层交替重叠形成一种“千层饼”结构。复合物中液晶结构的保持是物理缠结和化学交联的结果。     

Band texture formation of sheared polymeric liquid crystalline state

The phenomenon of band texture formation of sheared main chain liquid crystalline polymers is reviewed. The bands seen in a polarizing microscope are optical effects. The macromolecular chains are aggregated into zig-zag bent fibrils perpendicular to the bands. The band texture is formed during shear relaxation. The induction period depends on the shear rate applied, the shearing time, solution concentration (lyotropic), solution layer thickness, temperature and the nature of the polymer. There exists a critical shear deformation to bring a multi-domain nematic or cholesteric phase into a monodomain continuous phase, from which the band texture is formed. These two phases show quite different rheological behavior. In certain cases randomly oriented regions of bands can also be formed during quenching of a thermotropic nematic polymer melt or during standing of a lyotropic nematic polymer solution, where the nematic domains in the melt or in the solution have grown to a sufficient size.     

Optical properties of a shear-deformed thermotropic cellulose derivative

The band texture of a thermotropic cellulose derivative, trifluoroacetoxypropylcellulose, was studied by optical microscopy. The texture consists of parallel, long, thin, black lines when viewed between crossed polarizers with one polarizer parallel to the shear direction. These lines are perpendicular to the shear direction. Their optical properties indicate that the molecules are cooperatively oriented and this orientation director alternates from 0° to ±45° from the shear direction, with most of them at ±45°. This band phenomenon is identical to that observed with thermotropic nematic copolyesters.     

Alignment of liquid crystal molecules on oriented (E-CE)C/PAA films

A film of ethyl-cyanoethyl cellulose/polyacrylic acid, (E-CE)C/PAA, using an alignment layer of liquid crystal (5CB), was prepared by shearing and then photo-polymerization of an (E-CE)C/AA solution. The orientation of the (E-CE)C chains in the sheared film and the alignment of the 5CB molecules on the films were investigated by polarizing optical microscopy and FTIR. It was found that the (E-CE)C/PAA oriented film showed perfect alignment ability for the 5CB molecules. The director of the 5CB molecules on the oriented film does not lie along the orientation direction of the (E-CE)C main chains, but inclines to that of the (E-CE)C main chains. The direction of the 5CB molecular orientation on the (E-CE)C/PAA oriented film is influenced by the degree of orientation of the (E-CE)C chains in the oriented film.