乙基醋酸纤维素液晶态的结构形态

本文利用偏光显微镜、电镜、小角激光光散射(SALS)和X-射线衍射仪研究了乙基醋酸纤维素溶致性液晶态从非平衡到平衡过程的转变,同时研究了从液晶态结晶的固体形态。在两玻片之间受力的液晶溶液,需要一定的时间才能重新形成。主要以带状和球晶的形态存在,溶剂挥发以看,部分球晶发生变化,还观察到各区域的取向结构,并证实了从液晶态结晶的晶型与各向同性溶液结晶的晶型相同,但完整度不同。     

利用光学显微镜研究溶剂诱导的梯形苯基聚倍半硅氧烷结晶

通过溶剂诱导结晶的方法研究了梯形苯基聚倍半硅氧烷(PPSQ)的球晶结构. 采用光学显微镜研究了溶液的浓度、溶剂的挥发时间以及温度等影响因素对梯形苯基聚倍半硅氧烷的球晶结构形貌的影响. 实验结果表明:稀释溶液浓度与提高结晶温度在改变球晶的形态方面具有相同的效果. 球晶的尺寸会随着溶液浓度的降低或者结晶温度的升高而增加. 这都归因于梯形苯基聚倍半硅氧烷在二甲苯中的溶解度的增加. 在不改变其它结晶条件的情况下,延长溶剂的挥发时间也会形成更大的球晶. 当在光学显微镜下旋转样品时球晶的结构不会发生改变,这表明球晶具有均一的晶体学取向结构. 负性球晶的特征也表明梯形苯基聚倍半硅氧烷的分子链是沿着球晶的切线方向排列. 考虑到梯形苯基聚倍半硅氧烷具有刚性的分子链,还提出了梯形苯基聚倍半硅氧烷可能的球晶结构模型.     

聚对苯甲酰胺液晶态球晶生长机理

本文用热台偏光显微镜和透射电子显微镜研究了聚对苯甲酰胺(PBA)/H_2SO_4液晶态生长球晶的形态结构和结晶机理。结果表明,PBA/H_2SO_4向列型液晶相具有过冷状态,可达30—40℃左右,并可生长球晶结构,一般直径可达5毫米左右。20Wt％溶液在不同的过冷态结晶时,可以生成三种形态的球晶结构,这是由于构成球晶的基本结构单元——有序微区结构在不同过冷条件下堆砌排列的规整程度不同的缘故。球晶的形态结构只与过冷程度有关,而与溶液的浓度无关。同时还研究了变温和剪切应力下结晶的球晶形态。     

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。     

BTDA/m-PDA聚酰亚胺环带球晶形貌与生长影响因素的研究

综述了本课题组BTDA/m-PDA聚酰亚胺环带球晶研究的进展.通过偏光显微镜(PLM),透射电镜(TEM),和原子力显微镜(AFM),研究了球晶中片晶的生长形貌,并探讨了环带形成的机理.考察了环带球晶生长的影响因素,包括:(1)温度:在较低酰亚胺化温度下只能形成不规则的球晶,而在较高温度下形成中心环间距较大的球晶;(2)聚酰胺酸分子量:分子量较低聚酰胺酸不能形成环带球晶;(3)分子链的不对称性:通过不同比例单体共聚发现,分子链上间苯二胺和羰基的不对称性对环带的形成有着决定性的影响;(4)溶剂:随着溶剂含量的增加,环带球晶的环间距增大.     

聚醚醚酮球晶结构的形态特征研究

本文借助热台偏光显微镜,扫描电子显微镜,红外光谱等技术研究了聚醚醚酮(PEEK)球晶结构的形态特征。发现PEEK的同-球晶可在不同条件下呈现放射状及带状的形态,而这两种形态可相互进行可逆的热转变。对这两种球晶的相互转变规律及球晶的微观结构作了分析,提出了PEEK球晶结构的模型。     

尼龙1010环状球晶的研究

利用偏光显微镜研究了尼龙1010环状球晶的生成条件、形态特征和光学性质,发现在等温结晶过程中只可生成环状球晶;在降温过程中可由相同光性的放射状球晶转变成正、负、混合光性环状球晶;在升温过程中正光性和混合光性环状球晶分别转变成不对称四瓣形和六瓣形环状球晶,负放射球晶可转变成另一种负环状球晶。     

聚对苯二甲酸丁二酯熔融结晶形态的扫描电镜观察

本文利用扫描电镜和离子蚀刻技术研究了PBT熔融结晶的形态结构。结果表明,PBT根据其结晶条件的不同可产生非常结晶、正球晶、螺旋状球晶及树枝晶。非常球晶呈放射状织构,但晶的中部是由约0.2μ的晶带交织而成网状结构。正球晶呈放射状织构,结构比较紧密。螺旋状球晶虽然也有放射状织构,但放射状的片晶已有一定程度的扭曲,球晶的中部为不规则螺旋扭曲,这类球晶在偏光显微镜下没有观察到典型的黑十字消光图。     

插层聚合聚丙烯-蒙脱土纳米复合材料的微观结构形态

使用偏光显微镜，扫描电镜，透射电镜和广角X射线衍射法研究了插层聚合法制备的聚丙烯－蒙脱土（PP－MMT）纳米复合材料的微观结构和形态发展。结果表明，随着插层聚合反应的进行，较大的初级MMT粒子逐渐剥离成较小的次级粒子。次级粒子由2－20片的单个MMT片层组成，其层间充满了PP分子链。提出了插层聚合过程中PP－MMT复合材料的形态发展模型。另外，MMT的加入对PP的球晶形态也有重要影响，PP完整的球晶随MMT的加入逐渐变小和趋于扭曲甚至破坏。     

溶致性液晶高分子PBT的结构表征

聚苯撑苯并二噻唑(PBT)具有典型的溶致性液晶行为,聚合后期有液晶态搅拌乳光现象。偏光显微镜观察到具有向列型织态结构,溶液粘度随浓度变化,当进入液晶区时有明显的反常突变。对高分子链和凝聚态结构进行了X射线衍射研究,测定了晶胞参数、C轴等同周期和高分子链的取向度,并表明取向的PBT凝聚态是由刚性棒状的分子呈园柱体形态二维有序堆砌而成的。     

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.     

MORPHOLOGY OF A THERMOTROPIC AROMATIC POLYESTER

The crystalline morphology of a thermotropic aromatic polyester has been studied by microscopy techniques. Spherulites with ringed structure under polarizing micioscope were observed for solution cast specimens, They were composed of radially growing crystalline lamellae of thickness around 100. It was found that the molecules were packed in the thickness direction. Banded texture was observed in randomly packed domains for melt cast specimens. The bands have the same width and internal structure as those usually observed in oriented specimens of these polymers obtained by shearing their mesomorphic melt.     

Polymer analysis: Molecular structure and properties of industrial polymers

Low density polyethylenes made by the known high pressure processes show significantly different molecular structures. The physical and technological properties are closely related to molecular structure and morphology. For example, the adhesive strength of a laminate consisting of an ozone treated low density polyethylene film and an aluminum foil depends strongly on the synthesis conditions. The molecular structures and dilute solution properties of many fully aromatic thermotropic liquid crystalline copolyesters can now be determined using the new solvent 3,5-bis(trifluoromethyl)phenol. A typical random copolyester was fractionated by precipitation from solution, and the fractions were studied in detail by viscometry, integrated and dynamic light scattering, and size exclusion chromatography. From the structure data thus obtained the molecular mass distribution and the persistence length were calculated. Polymer blends, block copolymers, and graft copolymers can be characterized by fractionation procedures using demixing solvents in an ultracentrifuge and subsequent analysis of the fractions.     

LAMELLAR STRUCTURE OF THERMOTROPIC LIQUID CRYSTALLINE POLYMERS

The lamellar structure of a thermotropic aromatic polyester with flexible spacer has beenstudied by using transmission electron microscopy. It was found that the lamellar structure couldbe observed in the crystalline samples of this semirigid polymer crystallized from different states.The thickness of lamellae is around 10 nm, which is similar to that of the conventional polymersof flexible chain molecules. The molecular chains in the lamellae are oriented in the thicknessdirection as determined by electron diffraction. The possibility of molecular chains folding in the lamellae has been discussed.     

一种支氏液晶共聚酯的合成

在聚对苯二甲酸乙二醇酯与对羟基苯甲酸 (HBA)形成的共聚酯 (PET HBA)分子链中 ,引入具有分形结构的单体———三羟基苯 (TOP) ,以降低其熔点 ,改善加工性能 .考察乙酰化时间、缩聚时间、压力、TOP和HBA加入量对新型分形共聚酯的对数比浓粘度的影响规律 ,以及TOP和HBA加入量对新型分形共聚酯的熔点和液晶清亮点的影响 .TOP的加入能使PET HBA共聚酯的熔点下降 10℃以上 ,而液晶清亮点没有变化 ,拓宽了液晶区域     

The synthesis of mesogenic polymers provoked by molecular mobility. polysiloxanarylenes

An approach to the synthesis of potentially thermotropic liquid crystalline polymers based on parallel investigation of their molecular mobility was realized. The initial idea was provoked by the observation that there exists some correspondence of molecular mobility data and the ability of a polymer to form a liquid crystalline phase. Previously this phenomenon was demonstrated on the example of a series of thermotropic main chain polymers with flexible dimethylsiloxane spacers of variable length. The relation between the structure of the main chain and local molecular mobility of different fragments was investigated in a series of regular polysiloxane-silarylenes containing rigid aromatic sequences. Molecular mobility was studied by dielectric spectroscopy in solution and in solid state. The structure of the main chain has been changed by variation of the repeated fragments' length, substituents and joint groups. The data of molecular mobility and their conformity with the chain structure were used for directed synthetic search of desired mesogenic polymers.     

Morphology and interference color in spherulite of poly(trimethylene terephthalate) copolyester with bulky linking pendent group

A novel phosphorus-containing copolyester (PTTP), poly(trimethylene terephthalate) (PTT) copolyester with a bulky linking pendent group of 9,10-dihydro-10-[2,3-di(hydroxycarbonyl) propyl]-10-phosphaphenanthrene-10-oxide (DDP) was prepared, and its crystallization, crystal morphology and interference color were investigated in this article for the first time. Differential scanning calorimeter (DSC) results showed that with the increase of DDP content, the melting point (T(m)) and crystallization ability of PTTP decreased. WAXD results suggests that the three samples share one crystal structure, however the crystallinity decreases with increasing DDP content. Polarized optical microscope (POM) observation indicated that the samples showed non-banded spherulites at a lower and higher temperature, and banded spherulites at the middle temperature range. From the micrographs obtained from scanning electronic microscopy (SEM) and atomic force microscopy (AFM), ringed patterns with many defects could be found for samples with higher DDP contents, which crystallized at a lower temperature, and a transformation from square-shaped spherulites to circular spherulites was noted for samples with higher DDP contents, which crystallized at a higher temperature. The interference color of the spherulites was also studied and it was shown that with the increase of film thickness or decrease of DDP content, the spherulites became more colorful under POM observation, indicating that the hindering effect and randomness caused by incorporating the DDP monomer with a bulky pendent group into the PTT molecular chain exhibited a negative influence on the molecular mobility and crystallization ability of the copolyester, and led to the formation of the defective band morphology and the less colorful interference color of the PTTP spherulites.     

Characterization of a melt processable liquid crystal copolyester

Poly[oxy(2-methyl-1,4-phenylene)oxyterephthaloyl-co-oxymethylene-1,4-cyclohexylene-methyleneoxyterephthaloyl] was synthesized using a solution-based process. This copolyester has cyclohexylene dimethylene as a semi-rigid spacer along the polymer main chain to interrupt the inherent rigidity of the system while preserving the mesogenicity of the macromolecules. Polymer characterization includes elemental analysis, Fourier transform infrared spectroscopy, nuclear magnetic resonance, hot-stage polarized light microscopy, wide-angle x-ray diffraction, dilute solution viscometry, differential scanning calorimetry, and thermogravimetric analysis. This copolyester shows nematic liquid crystalline behavior in polarized light above about 240°C. The intrinsic and inherent viscosities are 0.88 and 0.68 dL/g respectively. The observed melting temperature of this copolyester is about 265°C, but melting begins as low as 215°C, making the polymer readily melt-processable. The degradation temperature is about 340°C under a nitrogen atmosphere. © 1995 John Wiley & Sons, Inc.     

全芳香族共聚酯的结构和其液晶行为研究

本文对不同组成的对苯二甲酸(TPA),对羟基苯甲酸(PHBA),联苯二酚(BP),间苯二甲酸(IPA)共聚酯采用热台偏光显微镜、电子显微镜、X-射线衍射、激光小角散射、差热等技术进行了研究.实验结果表明,在一定的组成范围内共聚酯熔体有很好的液晶性.重点讨论了分子组成、转变行为、液晶性的关系,并对液晶相的形态结构进行了表征.     

Synthesis and characterization of a series of thermotropic liquid crystalline copolyester nanocomposites

A series of aromatic thermotropic liquid crystalline copolyester (TLCP) nanocomposites were prepared by the in situ intercalation polymerization of p‐acetoxybenzoic acid (ABA), terephthalic acid (TPA), and diacetoxynaphthalene (DAN) isomers in the presence of the organoclay. The DAN isomers used in this study were 2,3‐ and 2,7‐naphthylene. We examined the variation of the liquid crystallinity, morphology, and thermal properties of the nanocomposites with organoclay content in the range 0–10 wt %. All the polymer nanocomposites were fabricated with a molar ratio of ABA:TPA:DAN = 2:1:1; they were shown to consist of a nematic liquid crystalline phase for low organoclay contents (≤5 wt %), whereas the hybrids with a higher concentration of organoclay (≥10 wt %) were found not to be mesomorphic. By using transmission electron microscopy, the clay layers in the 2,3‐DAN copolyester hybrids were found to be better dispersed in the matrix polymer than those in the 2,7‐DAN copolyester hybrids. The introduction of an organoclay into the matrix polymer was found to improve the thermal properties of the 2,3‐DAN copolyester hybrids. However, the thermal properties of the 2,7‐DAN copolyester hybrids were found to be worse than those of the pure matrix polymer for all organoclay compositions tested. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 387–397, 2006