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。     

热处理对溶致性液晶高分子PBT薄膜结构和性能的影响

聚苯撑苯并二噻唑(PBT)薄膜是由液晶相溶液在应力下制成的,主要用作结构材料或复合材料的增强剂。本文对不同条件下热处理的PBT膜进行了FTIR、广角X-射线衍射、元素分析和力学性能的测定研究,证明了热处理能进一步完成关环反应,使分子链结构更规整,凝聚态结构更有序,明显地提高材料的力学性能和热稳定性,并提出了最佳的热处理温度。     

碘掺杂和非掺杂高取向反式聚乙炔导电性能的各向异性

本文应用量子化学EHMO/CO方法计算了高取向反式聚乙炔及其碘掺杂物的二维能带结构,并以此为依据讨论了它们导电性能的各向异性.平行于分子链方向的电导率与垂直于该方向的电导率之比(σ_■,/σ_⊥)取决于这两个方向上价带宽和导带宽的大小.碘掺杂后σ_■/σ_⊥下降,其原因是链间耦合增强的结果.这也使掺杂后的反式聚乙炔成为链间相互作用微弱的三维体系.计算结果与实验结果较好地吻合.     

热致液晶含氯侧基聚芳醚酮的单晶状条带织构

通常主链液晶高分子在受到剪切作用时 ,分子微纤呈周期性锯齿状排列 ,其光学效应表现为在偏光显微镜下可观察到相互平行且与剪切方向垂直的条带织构 [1] .而厚度适中的主链液晶聚合物薄膜经过热处理 ,即使没有受到剪切取向的作用 ,介晶微区的尺寸发展到一定大小时也会形成条带织构 ,即所谓结晶诱导[2 ] 和固化诱导 [3,4 ] 的条带织构 .在所报道的条带织构中 (包括剪切和非剪切 ) ,分子链均平行于膜平面 .本文研究发现 ,热致液晶氯代聚芳醚酮的薄膜样品在其高有序液晶温区经热处理 ,可形成结晶诱导的单晶状条带织构 ,其分子链垂直于膜平面 .…     

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。     

溴和碘掺杂高取向反式聚乙炔导电性能各向异性研究

根据固体能带理论,用EHMO/CO方法,计算了高取向反式聚乙炔及溴和碘掺杂态的二维能带结构,讨论了其导电性能的各向异性.研究表明,平行和垂直于分子链方向的电导率之比(σ_///σ_⊥上)取决于这两个方向上能隙和带宽的大小掺杂后σ_///σ_⊥下降是由于掺杂剂使链间栖合作用增强所致.理论计算与实验结果一致.     

界面单分子膜的共振Raman光谱及分子取向分布

基于长链分子在界面单分子膜中的单轴取向性,建立了以分布函数描述的取向分布模型。籍此对含偶氮苯的长链两亲性分子的界面单分子膜的共振Raman光谱观测结果进行了理论分析。利用偏振Raman强度值计算得到序参数和,并进一步给出了分子取向分布的图象。结果表明,取向分布随吸附量增加而改变,在不同的界面间显示出有意义的差别。文中还从分子取向变化的角度,讨论了二维凝聚态的性质,从而对这类界面体系获得更深刻的认识。     

超高分子量聚乙烯凝胶膜超高取向过程的几个不同阶段

通过Ｘ射线衍射、平板照相、扫描电镜等方法观测超高分子量聚乙烯凝胶／结晶膜取向过程中的结构形态变化，并根据ＰＥ片晶分子动力学模拟结果，提出ＵＨＭＷＰＥ凝胶膜在热拉伸取向过程中明显存在３个不同阶段，即：初期片晶转动或滑移，ｂ轴优先垂直于拉伸方向取向；随着拉伸比增大，片晶的ｃ轴平等于伸方向，同时，分子链的解折叠开始，部分非晶链也进入伸直链区取向，当拉伸比达到极限倍率时，分子链已经接近完全伸展成为比较刚直     

n-型掺杂反式聚乙炔导电性能各向异性研究

根据固体能带理论，用量子化学ＥＨＭＯ／ ＣＯ 方法，计算了高取向反式聚乙炔及其ｎ－ 型掺杂态（掺杂Ｌｉ，Ｎａ，Ｋ） 的二维能带结构，首次从能隙与带宽角度讨论了聚乙炔经ｎ－ 型掺杂呈现的导电性能的各向异性．研究表明：平行和垂直于分子链方向的电导率之比（σ∥／σ⊥） 取决于这两个方向上能隙和带宽的大小；掺杂后σ∥／σ⊥下降，其原因是掺杂剂在聚乙炔链间架起了一个“浮桥”，使链间耦合作用增强．理论计算与实验结果一致     

高取向顺式聚乙炔导电性能的各向异性

用ＥＨＭＯ／ＣＯ方法计算了高取向顺式聚乙炔及其碘掺杂物的二维能带结构，并据此讨论了它们导电性能的各向异性问题，结果表明平行于分子链方向的导电率与垂直于该方向的电导率之比（σ‖／σ⊥）取决于这两个方向上的价带宽和导带宽。碘掺杂后σ‖／σ⊥下降的原因是链间耦合增加。碘掺杂后的顺式聚乙炔是一个链间相互作用微弱的的二维或三维体系。计算结果与实验较好地吻合。     

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.     

Crystal structure of friction-transferred poly(2,5-dioctyloxy-1,4-phenylenevinylene)

Poly(2,5-dioctyloxy-1,4-phenylenevinylene) (DOPPV) was found to form a highly oriented film by a friction-transfer technique. Structural investigation of friction-transferred DOPPV was studied by means of polarized ultraviolet-visible (UV-vis) absorption spectroscopy, polarized photoluminescence (PL) spectroscopy, and synchrotron-sourced grazing incident X-ray diffraction (GIXD) analysis. The polarized UV-vis absorption and PL spectra indicate clear axial alignment. DOPPV backbones in friction-transferred film are highly aligned along the drawing direction of the friction-transfer. Further information of the molecular arrangement in friction-transferred DOPPV film was investigated by both the out-of-plane and the in-plane GIXD analyses with synchrotron source. The DOPPV molecules in friction-transferred films were perfectly arranged three-dimensionally: the backbones aligned along the drawing direction of friction-transfer, the alkyl side chains lay in the film plane, and the planar backbones were arranged parallel to the film surface. Additionally, two neighboring DOPPV molecules along the direction of inter-backbones separation by alkyl side chains were found to be shifted with respect to one another by the mean distance of half of a monomeric repeat.     

用偏振红外光谱表征经单轴和双轴拉伸的PET薄膜

用偏振红外光谱方法研究了拉伸速率和不同拉伸方式,包括单轴拉伸、双轴同时拉伸和双轴依次拉伸等,对PET薄膜取向的影响。对由不同拉伸方式制得的反式结构含量和密度均基本相同的试样进行比较得出:单轴拉伸试样中分子链相对拉伸方向的轴取向程度最高,分子链在薄膜平面内的取向分布亦最不均匀;双轴拉伸试样中分子平面(苯环面)相对薄膜平面有明显的平面取向,而单轴拉伸试样中分子平面和薄膜平面基本上无共平面趋势。在所用的实验条件下,拉伸速率对取向程度几乎没有影响。     

Thickness-dependent molecular chain and lamellar crystal orientation in ultrathin poly(di-n-hexylsilane) films

The molecular chain and lamellar crystal orientation in ultrathin films (thickness < 100 nm) of poly-(di-n-hexylsilane) (PDHS) on silicon wafer substrates have been investigated by using transmission electronic microscopy, wide-angle X-ray diffraction, atomic force microscopy, and UV absorption spectroscopy. PDHS showed a film thickness-dependent molecular chain and lamellar crystal orientation. Lamellar crystals grew preferentially in flat-on orientation in the monolayer ultrathin films of PDHS, i.e., the silicon backbones were oriented along the surface-normal direction. By contrast, the orientation of lamellar crystals was preferentially edge-on in ultrathin films thicker than ca. 13 nm, i.e., the silicon backbones were oriented parallel to the substrate surface. We interpret the different orientations of molecular chain and lamellar crystal as due to the reduction of the entropy of the polymer chain near the substrate surface and the particularity of the crystallographic (001) plane of flat-on lamellae, respectively. A remarkable influence of the orientations of the silicon backbone on the UV absorption of these PDHS ultrathin films was observed due to the one-dimensional nature of sigma-electrons delocalized along the silicon backbone. With the silicon backbones perpendicular or parallel to the surface of the substrate, the UV absorbance increased or decreased with an increase of the angle between the incident UV beam direction and direction normal to the thin film, respectively.     

The effect of melt processing conditions on the hydrogen-bonded sheet orientation and polarization of nylon 11 films

It is known that melt-quenched, cold-drawn, and then annealed nylon 11 films possess a particular doubly oriented hydrogen-bonded sheet structure: the hydrogen-bonded sheets being in the plane of the film and the molecular chain direction being in the direction of draw. These films have been shown to be ferroelectric. In order to clarify the role of this special double orientation on polarization mechanisms and, in addition, provide insight into the reasons for this unique orientation, a systematic study was undertaken. Nylon 11 was melted at 210°C in a hot press for different melting times (ranging from 30 s to 20 min) prior to quenching into an ice-water bath. The resulting orientation of the hydrogen-bonded sheet structure in these films was examined using wide-angle X-ray diffraction and FTIR spectroscopy. For undrawn, melt-quenched films with short times in the melt, a degree of preferred orientation of the hydrogen-bonded sheets in the plane of the film was observed. As time in the melt increased, this preferred orientation in the plane decreased. This was also observed for films which were cold drawn before annealing. However, following cold drawing and several cycles of polarization using a maximum field of 150 MV/m at room temperature, the uniaxially drawn films with different times in the melt possessed the same remanent polarization and the same final orientation of the hydrogen-bonded sheets in the film thickness direction. © 1996 John Wiley & Sons, Inc.     

Highly ordered polymer films of amphiphilic, regioregular polythiophene derivatives

The fabrication and characterization of highly ordered thin films made from amphiphilic, regioregular polythiophene derivatives are described. Films of poly(3-(11-(2-tetrahydropyranyloxy)undecyl)thiophene (PTHPUDT) were prepared by the Langmuir-Blodgett technique. The amphiphilic nature of the polymer affords layer-by-layer deposition and the formation of multilayer films of head-to-head and tail-to-tail Y-type structure. X-ray diffraction studies indicate bilayer separations of approximately 30 A. Anisotropic optical absorption in the plane of the film indicates that the thiophene backbones are preferentially oriented along the dipping direction. Further, polarized light microscopy studies indicate that these films are highly birefringent and that the optical retardation is uniform over the entire film. Ellipsometry studies confirm the sizable magnitude of the birefringence. Optical second-harmonic generation studies of multilayer films provide information regarding both the thiophene orientation within the film and the anisotropic distribution of chromophores in the surface plane. Taken together, these data offer strong evidence of highly ordered films in which the hydrophobic polythiophene chains lie parallel to the substrate surface with their alkyl chains oriented normal to the surface, as dictated by the hydrophilic nature of the alkyl chain's terminal tetrahydropyran functional group. As such, these films offer the potential for elucidating the connection between polymer morphology and physical property in materials that are otherwise subject to a sufficiently complex distribution of morphologies that such a correspondence is precluded.     

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.     

间同立构1,2-聚丁二烯的合成和形态结构研究

间同立构 1 ,2 -聚丁二烯自 1 955年问世以来 ,引起人们的广泛关注 ,但绝大多数研究工作集中在聚合物的合成方面[1～ 3] ,对其形态结构方面的研究却很少报道[4 ] ,原因是该聚合物分子侧链含有大量双链 ,在较高温度下 (>1 50℃ )很容易产生热交联 ,这给结构研究造成了很大困难 .间同立构 1 ,2 -聚丁二烯的性能取决于间规度 ,低间规度聚合物呈现弹性体特征 ,而高间规度聚合物则是一种半结晶性塑料 ,其结晶为平面锯齿链正交堆砌 ,Pacm空间群[4 ] .本文采用一种新的催化体系 ,使合成的 1 ,2 -聚丁二烯间规度可以调控 .同时首次报道了结晶性间规…     

Phase Transition and Structural Investigations in 50.5, 50.6 and 50.7

We report X-ray diffraction, density, ultrasonic velocity and refractive index studies in the N(p-n-pentyloxy benzylidene) p-n-alkylaniline compounds, viz. 50.5, 50.6 and 50.7. The nematic-smectic A (NA) transition is found to be weak first order in 50.6 while it is second order in 50.5 and 50.7. The salient features observed are cybotactic clusters in the nematic phase in all the compounds, molecular tilt which was inferred due to the end alkyl chains tilt causing orienta-tional disorder (smaller orientational order parameters 's' than expected) in smectic A phase, smectic F phase and large tilt angle variation in smectic C phase in a small temperature range in 50.5. The observed results are discussed in the light of available data in other n0.m compounds.