条带织构装饰技术观察含T─型液晶基元的热致性聚芳酯液晶态的向错

采用条带织构装饰新技术研究了含Ｔ─型液晶基元的热致性聚芳酯液晶态的向错形态．经过培养的液晶样品无需剪切，淬火后便可呈现出围绕向错点取向排列的条带织构，而条带织构长轴的垂直方向正代表了液晶基元的指向矢方向，这样，在普通偏光显微镜下就能直接观察到这些条带织构装饰的强度Ｓ＝±１／２和Ｓ＝±１的向错，并观察到Ｓ＝－３／２的高强度向错和闭环状的反转壁．     

片晶装饰技术研究高分子液晶向列相的向错

采用片晶装饰技术和四氧化钉染色技术相结合在透射电镜下研究了热致性高分子液晶的向错结构，在一种热致性聚芳酯的冻结液晶态中观察到了向错强度分别为Ｓ＝±１／２和Ｓ＝±１的两类共六种的向错形态，以及每个向错与其相邻向错之间相互联结和相互作用的状态．     

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。     

主链型高分子液晶向列相向错观察的进展

综述了主链型高分子液晶向列相向错在实验观察方面的进展。从纹影织构的观察和展曲、弯曲弹性常数相等条件下的二维曲率弹性理论出发探讨了向错结构的几何特征。简要涉及了弹性常数不相等对向错的影响、向错核心的本质和反转墙的观察;给出了拓扑强度s高达4的高阶向错的实验观察结果;归纳出描绘向错周围指向矢场的主要实验方法:1)片晶装饰;2)条带织构装饰;3)表面微裂纹装饰。本文对上述方法进行了讨论和比较,列举了一些电子显微镜和光学显微镜照像的图例。     

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．     

某些含二维液晶基元的热致液晶高分子的向列态纹影织构

发现某些含二维液晶基元的热致液晶高分子容易产生反向壁织构与含有高强度向错点(|S|大于1)的向列态纹影织构。这类液晶高分子的织构与形态学特点与含一维棒状液晶基元的其他液晶高分子不同。     

某些含二维液晶基元的热致液晶高分子的向列态纹影响构

发现某些含二维液晶基元的热致液晶高分子容易产生反向壁织构与含有高强度有错点（│Ｓ│大于１）的向列态纹影织构。这类液晶高分子的织构与形态学特点与含一维棒状液晶基元的其他液晶高分子不同。     

新型热致型液晶苯代聚芳醚酮的单畴液晶行为

通过偏光显微镜研究了在外力场作用下新型热致型液晶苯代聚芳醚酮的向列相单畴液晶行为。结果表明，聚合物在剪切力作用下形成条带织构，强外力场能使介晶基元沿基质表面平行排列，形成均匀织构的单畴区。由于裂纹的存在，观察到了四条和六条黑刷的纹影织构。     

近晶C(Sc)相串型液晶高分子的合成与表征

以２，５ 二（对烷氧基苯甲酰氧基） 对苯二酚和不同结构的脂族二酰氯为单体，采用低温溶液缩聚的方法，合成了一系列新的液晶基元垂直于分子主链的Ｓｃ相串型液晶高分子．单体的结构通过元素分析、ＩＲ、１Ｈ ＮＭＲ和ＭＳ等方法确证．聚合物通过ＧＰＣ、ＤＳＣ、ＴＧ、ＷＡＸＤ和偏光显微镜等方法测试表征．研究发现，所有的聚合物加热至各自的熔点以上都能形成液晶态，在液晶态可以观察到纹影或焦锥织构．通过变温Ｘ 射线衍射证明它们为Ｓｃ相．所有聚合物的熔点（Ｔｍ）和液晶态的清亮点（Ｔ１）随分子中末端烷氧基增大和柔性间隔段长度增加逐渐降低，液晶态温度范围变窄．     

一系列含T-型二维液晶基元的液晶高分子配体的合成

以４,４′ （α,ω 亚烷基二酰氧）二苯甲酰氯和２,４ 二羟基 ４′ 烷氧基偶氮苯为单体,通过溶液聚合,合成了一系列新的含Ｔ 型二维液晶基元的液晶高分子配体．单体的结构通过元素分析、ＩＲ、１Ｈ ＮＭＲ和ＭＳ等方法确证．高分子配体通过ＧＰＣ、ＤＳＣ、ＴＧ、ＷＡＸＤ和偏光显微镜等方法测试表征,发现所有的高分子配体加热至各自的熔点以上都能形成液晶态,在液晶态可以观察到向列型的丝状织构和纹影织构．它们的熔点（Ｔｍ）和液晶态的清亮点（Ｔｉ）随分子中末端烷氧基增大和柔性间隔段长度增加呈规律性变化．特别值得一提的是,发现末端不含取代基的高分子配体也能产生液晶态,这对该类高分子液晶态生成的机制与液晶态的织构提供了一个新的研究课题［１］．     

Direct decoration of disclinations by solidification-induced band texture for a nematic side chain liquid crystalline polymer

For a nematic polymethacrylate side chain liquid crystalline polymer, g 154 N 298 I (°C), the solidification-induced band texture has been observed aligned along the disclination under a polarizing optical microscope, when the specimen was quenched from 280°C to room temperature. The decoration technique of solidification-induced band texture, which is usually reported for main chain liquid crystalline polymers, was then introduced to reveal the director field pattern along a disclination for this side chain liquid crystalline polymer. It was found by infra-red dichroism measurements that the director orientation is parallel with the direction of the band. On this basis, disclinations with strength s=±1/2 and s=±1 were mapped according to the corresponding pattern of solidification-induced band texture. In addition, two types of inversion wall, loop-like and splay-type walls, were also found to be decorated by the solidification-induced band texture.     

Direct decoration of disclinations by solidification-induced band texture and focal-conic texture for a low molar mass liquid crystal

Two decoration methods, solidification-induced band texture decoration and focal-conic texture decoration, were established to map the director field of disclinations in a low molar mass methacrylate liquid crystal. It was found that when the specimen film is quenched from the nematic melt to room temperature, solidification-induced band texture is observed arrayed along with the schlieren texture, and the orientation of the director field can be displayed. Moreover, when the specimen is cooled from the nematic melt to 63°C and annealed, the focal-conic texture of the smectic A phase is found to grow around the corresponding disclination core with good orientation to reveal the director field. By the two decoration techniques, the director fields of disclinations with strength s = 1/2 and s = ± 1 were revealed. Two types of inversion wall, loop-like wall and splay-type wall, were found by both solidification-induced band texture decoration and focal-conic texture decoration.     

Banded texture decoration of disclinations in a main chain thermotropic aromatic copolyester observed by optical microscopy

A new method for the study of texture and director patterns in a main chain thermotropic aromatic copolyester with a flexible spacer is described, whereby the molecular chain or director orientation of the nematic mesophase becomes decorated by the formation of a banded texture during quenching, without being subjected to a shear. The pattern of the decorated banded texture may be observed directly by polarizing optical microscopy, revealing the complete texture of molecular chain orientation across the whole specimen. The molecular director orientation lies perpendicular to the long axis of the bands. Various types of disclination, including an inversion wall, in the nematic mesophase of a thermotropic aromatic copolyester have been observed. This decorating technique is particularly suited for non-crystallizable main chain liquid crystalline polymers, where the lamellar decoration technique fails.     

Direct decoration of disclinations by solidification-induced band texture and focal-conic texture for a low molar mass liquid crystal

Two decoration methods, solidification-induced band texture decoration and focal-conic texture decoration, were established to map the director field of disclinations in a low molar mass methacrylate liquid crystal. It was found that when the specimen film is quenched from the nematic melt to room temperature, solidification-induced band texture is observed arrayed along with the schlieren texture, and the orientation of the director field can be displayed. Moreover, when the specimen is cooled from the nematic melt to 63°C and annealed, the focal-conic texture of the smectic A phase is found to grow around the corresponding disclination core with good orientation to reveal the director field. By the two decoration techniques, the director fields of disclinations with strength s = 1/2 and s = ±1 were revealed. Two types of inversion wall, loop-like wall and splay-type wall, were found by both solidification-induced band texture decoration and focal-conic texture decoration.     

芳香共聚酯B-N多种向列织构的形态研究

从一种聚芳酯B-N得到了丝状(包括细丝和粗丝)、纹影状和大理石纹状等与小分子向列液晶相似的多种织构。由于样品淬火后晶片装饰在织构上而不影响分子取向矢的分布,因而可以用化学刻蚀和电镜技术揭示其向错和取向矢图。电镜和光学显微镜的结果相互补充,表明了细丝和粗丝状织构的分子取向矢分布很不相同,是两种不同的织构,而粗化始于第二熔融降温。在这些向列织构中分别发现了S=±(1/2)和s=+1的向错的例子和平面内微区转向壁的证据。     

Direct observation of director fields of disclinations in the nematic mesophase of a main chain thermotropic aromatic polyester by surface microcrack decoration

For a main chain thermotropic aromatic polyester with a flexible spacer, Cr 194 N 245 I (°C), the director fields around disclinations in the nematic mesophase can be decorated by both the solidification-induced band texture and surface microcracks. Director fields of various types of disclinations, including inversion walls, in the nematic mesophase of this semi-rigid polyester have been observed directly by polarizing optical microscopy. It was found that when the polymer was pre-sheared in the nematic state and then quenched to room temperature, a shear-induced band texture was observed, which relaxed slowly during annealing at 200°C, and then on quenching the solidification-induced band texture and surface microcracks appeared, displaying the pattern of the disclination fields. Pre-shearing is a necessary condition for the appearance of microcracks. On annealing, disclinations of various types were generated, quite often connected by inversion walls in the direction of pre-shearing. In some areas of the specimen where the shear-induced bands had not been completely relaxed during annealing, the shear-induced band texture was shown by the birefringence and surface microcracks to have a supermolecular structure of sinusoidal chain fibrils.     

芳香共聚酯B-N多种向列织构的形态研究

 从一种聚芳酯B-N得到了丝状(包括细丝和粗丝)、纹影状和大理石纹状等与小分子向列液晶相似的多种织构。由于样品淬火后晶片装饰在织构上而不影响分子取向矢的分布,因而可以用化学刻蚀和电镜技术揭示其向错和取向矢图。电镜和光学显微镜的结果相互补充,表明了细丝和粗丝状织构的分子取向矢分布很不相同,是两种不同的织构,而粗化始于第二熔融降温。在这些向列织构中分别发现了S=±(1/2)和s=+1的向错的例子和平面内微区转向壁的证据。     

Direct observation of director fields of disclinations in the nematic mesophase of a main chain thermotropic aromatic polyester by surface microcrack decoration

For a main chain thermotropic aromatic polyester with a flexible spacer, Cr 194 N 245 I (°C), the director fields around disclinations in the nematic mesophase can be decorated by both the solidification-induced band texture and surface microcracks. Director fields of various types of disclinations, including inversion walls, in the nematic mesophase of this semi-rigid polyester have been observed directly by polarizing optical microscopy. It was found that when the polymer was pre-sheared in the nematic state and then quenched to room temperature, a shear-induced band texture was observed, which relaxed slowly during annealing at 200°C, and then on quenching the solidification-induced band texture and surface microcracks appeared, displaying the pattern of the disclination fields. Pre-shearing is a necessary condition for the appearance of microcracks. On annealing, disclinations of various types were generated, quite often connected by inversion walls in the direction of pre-shearing. In some areas of the specimen where the shear-induced bands had not been completely relaxed during annealing, the shear-induced band texture was shown by the birefringence and surface microcracks to have a supermolecular structure of sinusoidal chain fibrils.     

Surface microcracks decoration and disclination defects of wholly aromatic liquid crystalline copolyesters

An intensive study has been conducted to map the director fields of disclination of nematic liquid crystalline copolyesters. In this study, films of two wholly aromatic main-chain polyesters containing para- (ABA/MH/TFTA) and meta-linkages (ABA/MH/TFIA) (ABA, p-acetoxybenzoic acid; MH, maleic hydrazine; TFTA, tetrafluoroterephthalic acid; TFIA, tetrafluoroisophthalic acid) were synthesized to investigate the effects of kinks on liquid crystallinity, disclination strength (S), and surface microcracks decoration. These two copolyesters were prepared by in-situ thin film polymerization and characterized by polarizing light microscope, wide-angle X-ray diffraction, as well as "rotational isomeric states" (RIS) Metropolis Monte Carlo (RMMC) simulation. An optical microscope shows that the surface microcracks forms in the nematic-mosaic texture during a rapid quenching. The ABA/MH/TFTA film exhibits disclination strength with S = +1 and S = -(1)/(2); however, disclination strengths with S = +/-1 have been observed in the ABA/MH/TFIA system. To our best knowledge, this is the first paper reporting the effects and evidence of kink (meta and para moieties) on topological defect of disclination. In addition, the RMMC analysis supports the liquid crystal formation in both polyester films with a persistence ratio greater than 6.42.