激光诱民聚酰亚胺纳米微结构中分子链取向排列的研究

通过Ｎｄ：ＹＡＧ偏振脉冲激光辐射聚酰亚胺薄膜,在其表面制得大面积纳米级周藏一微线条,线条的周期性为２００ｎｍ,线条方向始终平行于偏振激束电场方向,线条横截面为圆形或椭的柱状稔胍射红外光谱分别在平行与垂直纳米线条的方向上测试聚合物表面ＩＲＫ结果发现,１７２２和１２３１ｃｍ＾－１处的吸收有明显的二向色性,表明二线条内聚合物分子链部分呈现取排列,且聚酰亚胺分子我边方向与微线条方向垂直。     

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 .…     

各向异性光交联作用对液晶在起伏光栅表面的取向影响

以含肉桂酸基团的光敏聚酰亚胺为"墨水",通过软印刷技术制备了一种新型的可进一步光交联的表面起伏光栅,研究了各向异性光交联对光栅热稳定性和光栅诱导液晶取向的影响.研究结果表明,在经过紫外光交联后,光栅的热稳定性有较大提高,在经过高于未交联聚酰亚胺的玻璃化转变温度31℃处理2 h后,光栅形貌未发生变化.曝光前后光栅都能诱导液晶分子在表面均一沿面排列.当线性偏振紫外光的偏振方向与光栅沟槽垂直时,光交联能促进光栅对液晶的定向能力,反之则降低的定向能力.通过改变辐照光的偏振方向,调节光栅深度,能控制液晶分子在光栅上的取向方向.将这种软印刷得到的光栅用作液晶定向层,不仅可具有更好的热稳定性和定向能力,还可以调节液晶分子在光栅上的取向方向,实现多畴取向.     

聚苯乙烯微球表面的聚集态结构和苯基堆砌

用扫描隧道显微镜(STM)研究微乳液聚合法制备的聚苯乙烯微球.STM图像显示这种聚苯乙烯微球的表面具有不同的聚集态结构.在表面的某些区域,聚合物链没有相互缠结现象,而是有序地堆积在一起.在适当的情况下,同一条链上的苯基还会堆砌起来,形成一种平行移位的结构,其类似于苯双分子的最稳定结构.还用STM研究了用苯溶胀过的聚苯乙烯粒子,并观察到了类似螺旋结构的聚合物链以及扭曲的聚合物链.在聚苯乙烯微球中,聚合物链段和苯基的有序堆砌状态的存在,是因为苯乙烯单体已经在微乳液内的某些区域堆砌成有序的状态.     

液晶聚合物的表面形貌光调控研究进展

光响应液晶聚合物具有良好的自组装特性与光调控性能,被广泛地应用于表面微纳结构的研究中。通过改变液晶分子的取向方式和有序参数,可以得到复杂多样的表面形貌,这在光学、生物学和机械控制等领域有较高的研究价值与应用前景。表面形貌调控的关键在于对其机理的深刻理解与把握:从液晶分子指向矢的角度来说,当液晶分子的有序参数减小时,会沿指向矢方向收缩,垂直指向矢方向膨胀,利用相邻域之间分子取向差异产生的侧向剪应力,可以构建具有表面起伏的微纳结构;从液晶聚合物产生自由体积的角度来说,紫外光照射时产生的自由体积会使薄膜密度下降,在偶氮苯可逆的反-顺-反异构化的动态过程中,会形成宏观表面起伏;从光诱导聚合物质量迁移的角度来说,光场的光强分布、偏振态以及光束的波前均会对材料的定向质量迁移产生影响;从光照使薄膜表面稳定性改变的角度来说,可以利用光聚合时薄膜的各向异性收缩产生褶皱,也可以通过应力释放对薄膜的表面褶皱形貌进行调控。因此,基于光诱导产生表面形貌变化的4种不同机理,对光控表面形貌的相关研究进展进行了回顾和总结,并展望了未来可能的发展方向,为后续进一步研究液晶聚合物的表面形貌调控及其功能化提供了参考。     

用GGA泛函方法研究苯分子在石墨(001)表面的吸附

采用GGA近似的PW91泛函,在周期性边界条件下,使用平面波基组和超软赝势,研究了一系列的苯分子在石墨表面的吸附构型.我们发现苯分子之间的相互作用对苯在石墨表面的吸附能有较大影响,平行和垂直吸附构型分别在3×4和2×4超元胞中得到最大的吸附能.由于垂直吸附的苯分子之间相互作用较强,因此在较大的覆盖度下,苯分子将倾向于垂直吸附在石墨的表面.     

聚乙炔掺杂导电的双向机制

提出了一种掺杂聚乙炔的双向导电机理。垂直聚乙炔分子链方向的电荷输运是通过掺杂原子(或分子)在链间振动实现的;平行分子链方向的电荷输运是通过电荷密度波的传播实现的。掺杂聚乙炔的电导率随掺杂剂与聚乙炔链之间电荷转移量的增大而增大。     

含氟基团对液晶垂直排列的作用

实验发现双酚A双肉桂酸酯和六氟双酚A双肉桂酸酯单体在线偏振紫外光作用下发生光交联,形成的薄膜对液晶分子的排列效果截然不同,分别诱导液晶分子沿面平行排列和垂直排列.红外光谱分析表明光交联的类型均为[2+2]环加成反应.利用原子力显微镜观察薄膜表面,没有发现明显的各向异性拓扑分布.通过测量非含氟和含氟两种交联膜的表面能大小,发现氟的引入使薄膜的表面能降低,同时表面能中的极性作用明显降低.实验结果表明,氟基团的引入导致液晶分子垂直排列.本文探讨了这种垂直排列的原因.     

石英晶体微天平在聚合物薄膜研究中的应用与展望

石英晶体微天平仪(QCM)具有高度的灵敏性,能够对石英晶片表面微痕量物质的变化产生响应,在分析科学研究中广泛应用.本文阐述了QCM的基本工作原理和应用基础方程,并在此基础上综述了近年来QCM在聚合物薄膜研究中的应用及研究进展,包括QCM对聚合物薄膜的厚度和力学性能的测量、QCM研究聚合物分子链在石英晶片表面的吸附过程和链构象变化、表面引发生长聚合物刷的动力学过程、基于功能聚合物薄膜和QCM的生物与化学传感器等,同时对QCM在聚合物薄膜研究领域的进一步深入应用进行了展望.     

模板表面对间规聚苯乙烯在纳米模板中结晶取向的影响

以偏振显微红外光谱方法研究间规聚苯乙烯（sPS）在阳极氧化铝（AAO）模板孔洞内的结晶取向行为。 以正己基三甲氧基硅烷修饰AAO模板孔洞表面,使其烷基化,探索表面性质对不同尺寸孔洞内sPS结晶取向的影响。 结果表明,sPS在255 ℃温度下结晶,而且随孔洞尺寸的减小,纳米孔洞内sPS分子链的垂直取向程度均降低,并且相同孔径尺寸下在表面烷基化的孔洞内sPS晶区分子链的垂直取向程度更低。 这些现象可归因于分子链与孔壁间相互作用的不同导致孔壁表面对晶核取向的诱导。     

Laser‐induced periodic surface structure on a polymer surface: The effect of a prerubbing treatment on the surface structure

The influence of the mechanical rubbing of a polyimide (PI) film on the laser‐induced periodic structure (LIPS) was demonstrated. The periodicity and amplitude of LIPS were greater when the rubbing direction was parallel to the laser polarization direction. The amplitude became small and the periodicity of LIPS did not show an obvious change when the rubbing direction was perpendicular to the laser polarization direction. The effect of the rubbing pretreatment on LIPS was explained on the basis of the wave‐guide effect of rubbing‐induced microgrooves on LIPS formation. The orientation of PI chains induced by mechanical rubbing was relaxed after laser irradiation, and a new orientation of PI chains was formed during the LIPS formation. When the rubbing direction was perpendicular to the laser polarization direction, the orientation of PI chains remained in the rubbing direction. The laser‐irradiated, perpendicularly rubbed PI surface could be used to verify the effects of surface morphologies and intermolecular interactions on liquid‐crystal alignment. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1273–1280, 2003     

LOCAL ELECTRIC FIELD EFFECT ON THE CHLOROPHYLL FLUORESCENCE

Abstract. Polarized absorption and fluorescence of chlorophyll a and bacteriochlorophyll solutions in nematic liquid crystal mixtures have been studied in the presence of an external electric field.
The electric field caused a reorientation of the pigment molecules as concluded from changes in the polarized absorption. However, no correlation was found between the change in the polarized absorption and the change in the polarized fluorescence as a function of the field strength. The field influence was much stronger than expected only from the molecular orientation. The fluorescence polarized parallel to the direction of the liquid crystal was found to increase, whereas the similarly polarized absorption decreases. As a whole, the fluorescence yield significantly increased. It is suggested that the additional electric field is reinforced by a local field, most probably due to a protonation of the liquid crystal molecules.
Charged solvent molecules are reoriented in an external electric field which changes the local electric field acting on chlorophylls. Similar changes in CHI fluorescence yield due to local electric field can be created in vivo by the shift of charged molecules present in surrounding pigments. Such effects can be at least partially responsible for slow induction of fluorescence phenomena.     

Polarized laser-induced photofragmentation studies of JKM-selected CH3I molecules: retention of orientation in optical and DC electric fields

The technique of linearly polarized laser-induced photofragmentation for the measurement of the degree of orientation of rotationally state-selected symmetric top molecules [Phys. Rev. Lett.59, 2951 (1987)] has been used to study the retention of molecular orientation in optical frequency AC and homogeneous DC electric fields. For CH₃I beams, state-selected by the electrostatic hexapole focuser in several specific low-J parent states, recoupling of the iodine nuclear spin with the molecular rotational angular momentum occurs rapidly in weak fields, leading to some loss of orientation, but the resulting degree of orientation (i.e., theM _F distribution) is retained in both DC and optical frequency electric fields. The direction of the orientation of the molecular axis can be inverted with 100% efficiency by changing the sign of the DC ‘orienting field’. The up/down asymmetry of the photofragment angular distribution can be observed with either parallel (vertical) or perpendicular (horizontal) laser polarization.     

INFLUENCE OF ELECTRIC FIELDS ON FLUORESCENCE QUENCHING OF CHLOROPHYLL a IN NEMATIC LIQUID CRYSTAL MATRIX

Abstract— An electric field enhances the yield of fluorescence of chlorophyll in a liquid crystal solvent. The presented data suggest that the electric field effect is caused by the decrease in the efficiency of fluorescence quenching by ions. Quenching of each polarized component of fluorescence of chlorophyll molecules oriented by the liquid crystal matrix is different. The relative increase in fluorescence yield due to the applied electric field is stronger for a fluorescence component polarized parallel to the direction of liquid crystal orientation than for the perpendicular component.     

硅胶表面结构的热稳定性研究

本文研究了热处理(200-1100℃)对自制的一种硅胶的表面结构的影响;测定了BET比表面(低温氮气吸附法)、孔体积、乙醇的吸附-脱附等温线,计算了孔径分布,求得了最可几Kelvin半径。结果表明,杂质的存在明显地降低硅胶的热稳定性。在发生熔结以前,孔径分布基本不变,当发生熔结时,孔半径显著减小。红外光谱的测定表明,随着热处理温度的升高,硅胶表面缔合羟基(～3500cm^-1)迅速减少,在～800°时已去除殆尽,而自由羟基(～3720cm^-1)减少缓慢,在1100℃时才迅速消失。X-射线衍射图表明,发生熔结后的硅胶显示有β-鳞石英的衍射峰,说明出现了有序晶相。对上述实验结果,文中作了初步的解释。     

Alignment control of liquid crystals on surface relief gratings

Liquid crystal alignment layers of a high T_g polymer containing an azobenzene moiety are prepared by photofabrication of a surface relief grating (SRG). The interference pattern of a circular and linearly polarized Ar⁺ laser beam generated the surface relief grating and the morphology was detected by atomic force microscope. The optical anisotropy of the films was investigated by polarizing optical microscopy. The orientation of the optical axis of the film mainly depends on the direction of the initial polarization plane. Nematic liquid crystals were aligned parallel to the direction of the grating, but the pretilt angles of the liquid crystals were nearly zero. Irradiation with homogeneous linearly polarized light could also align liquid crystals, but this alignment capability was weaker than that of the SRG film.     

Spontaneous polarization and electro-optic behaviour of a ferroelectric liquid crystal cell fabricated with polyimide Langmuir-Blodgett films

The spontaneous polarization and electro-optic response of ferroelectric liquid crystals (FLCs) were investigated in a cell fabricated with a polyimide alignment layer coated by the Langmuir-Blodgett method. The surface properties of the cured polyimide layers were monitored by contact angle measurement, and by FTIR spectroscopy and AFM for the orientation and surface roughness, respectively. The apparent spontaneous polarization of an FLC determined in a practical sandwich-cell depended on various conditions such as cell thickness, cooling rate from the smectic A to chiral smectic C phase, and deposition pressure. Electro-optic response and decay times of FLCs were also measured. Furthermore, the ions in the FLC mixture reduced the magnitude of the effective electric field, but had no effect at high frequency.     

ROLE OF ELECTRIC POLARIZATION IN THE THERMOLUMINESCENCE OF CHLOROPLASTS

Abstract Effect of an external electric field on thermoluminescence and thermodepolarization currents were studied in suspensions and dry films of pea chloroplasts. The external electric field was applied either during interrupted heating at a given temperature ("direct effect") or was "stored" in the sample during cooling in the range –25°C and –70°C ("electret effect").
It is shown that in chloroplast suspension both the luminescence burst upon "direct effect" and the new band peaking between –40°C and –50°C induced by the "electret effect" are accompanied by a preferential decrease in the intensity of the thermoluminescence band around +10°C.
A correlation was established between the polarized state of thylakoids and the thermoluminescence burst induced by the external field. In electret samples of chloroplast suspension the intensity of field induced low temperature thermoluminescence band under different experimental conditions varied in parallel with the intensity of thermodepolarization current. In dry films of chloroplasts, in addition to parallel changes in intensities of thermoluminescence and thermodepolarization current, also the peak positions shifted in the same manner when either humidity of samples or temperature of illumination and of application of external field were varied.
We conclude that the polarization state of thylakoid membrane, which can be governed by an external electric field, plays an important role in determining charge stabilization and recombination properties of photosynthetic units. Our results implicate that electric field induces conformational changes in the membranes which increases the frequency factor ascribed to the recombination processes.     

Stretching effect of linearly polarized Ar+ laser single-beam on azo polymer colloidal spheres

This work shows that a linearly polarized Ar+ laser single-beam irradiation can cause stretching deformation of azo polymer colloidal spheres along the polarization direction of the laser beam. An epoxy-based polymer, containing 4-amino-4'-carboxyazobenzene at each repeat unit, was used to construct the colloidal spheres. The colloidal spheres were prepared by gradual hydrophobic aggregation of the polymeric chains in a THF/H2O dispersion medium, which was induced by a steady increase in the water content. When the obtained colloidal spheres were exposed to the spatially filtered and collimated Ar+ laser beam (488 nm, 150 mW/cm2), the colloids were stretched along the polarization direction of the laser beam. In the testing period (20 min), the colloids were deformed continuously as the irradiation time increased. When 2D close-packed arrays of the colloidal spheres were irradiated by the polarized laser single-beam, the colloidal spheres were all uniformly stretched along the polarization direction of the laser beam. On the contrary, when the arrays were irradiated by the interfering p-polarized laser beams, only the colloidal spheres in the bright regions of the interference pattern were significantly deformed.     

Photorefractive effect of ferroelectric liquid crystals

This paper reviews our recent work on the photorefractive effect of ferroelectric liquid crystals (FLCs). The photorefractive effect is defined as the optical modulation of the refractive index of a medium as a result of a variety of processes. The interference of two laser beams in a photorefractive material establishes a refractive index grating. This phenomenon enables the creation of different types of photonic applications. FLCs exhibit fast electric field response, and the orientation of the molecular axis of FLCs changes its direction according to the change in direction of the spontaneous polarization (Ps). When two laser beams interfere in a photoconductive FLC, an orientational grating is formed. The mechanism of the formation of the grating is based on the response of the Ps to the photoinduced internal electric field. The time of formation of the refractive index grating is significantly shorter in FLC materials.