尼龙1010对乙基氰乙基纤维素液晶态的影响

在尼龙1010/乙基氰乙基纤维素/二氯乙酸体系中,尼龙1010/二氯乙酸溶液相与乙基氰乙基纤维素/二氯乙酸溶液相不相容,各自形成相区。在乙基氰乙基纤维索含量一定时,增加尼龙1010的量,使液晶相转变温度提高,液晶相的织构也由于乙基氰乙基纤维素/二氯乙酸溶液相的浓度的增大而发生变化。在受到切应力作用后,液晶溶液形成条带织构,条带的方向与应力方向垂直。随着取向的大分子链的松驰解取向,各条带中沿着大分子链取向的方向上出现许多暗带线.把条带分剖成约0.5-1.0μm长的小块。在足够长的时间后,在切应力的方向上形成许多较宽的带。这些带由许多基本相互平行并与宽带形成一角度的小细带组成。上述现象除了与取向大分子链的松弛有关外,可能还与尼龙1010/二氯乙酸溶液相和乙基氰乙基纤维素/二氯乙酸溶液相的相分离有关。     

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.     

Effects of external fields on macromolecular cholesteric phase

Effects of external fields such as magnetic field and boundary conditions on supramolecular structure, molecular arrangement and the texture of the ethyl-cyanoethyl cellulose cholesteric liquid crystalline solutions were investigated. It was found that the molecules of (E-CE)C are oriented to perpendicular to the magnetic field and the diamagnetic anisotropy of (E-CE)C is negative. With homeotropic anchoring boundary condition, the molecules are aggregated with focal-conics arrangement the molecules are aggregated with planar arrangement with homogeneous anchoring boundary condition. The effects of the external field on the orientation of the cholesteric phase were influenced by the concentration of the solution because the twist power of the cholesteric was varied with the concentration. And the effects are also restrains by the surface tension of the interphase.     

Concentration dependence of magnetic field effects on the ethyl-cyanoethyl cellulose/dichoroacetic acid cholesteric phase

The effects of an external magnetic field with intensity 9.4 T on the cholesteric phase in ethylcyanoethyl cellulose (E-CE)C]/dichloroacetic acid liquid crystalline solutions were investigated for different concentrations. It was found that the diamagnetic anisotropy of (E-CE)C is negative and the effect of the magnetic field on the orientation of the cholesteric phase is influenced by the concentration of the solution, because the liquid crystalline properties of the solutions vary with the concentration.     

Concentration dependence of magnetic field effects on the ethyl-cyanoethyl cellulose/dichoroacetic acid cholesteric phase

The effects of an external magnetic field with intensity 9.4 T on the cholesteric phase in ethylcyanoethyl cellulose (E-CE)C]/dichloroacetic acid liquid crystalline solutions were investigated for different concentrations. It was found that the diamagnetic anisotropy of (E-CE)C is negative and the effect of the magnetic field on the orientation of the cholesteric phase is influenced by the concentration of the solution, because the liquid crystalline properties of the solutions vary with the concentration.     

磁场对乙基纤维素胆甾型液晶相的影响

高分子胆甾型液晶相是一个在高分子和液晶领域都引起广泛兴趣的课题,不仅因为自然界中的多种生物大分子,如纤维素,多肽,DNA等可以形成胆甾型液晶相;而且由于胆甾相具有特殊的螺旋结构(如图1所示),能产生一些特殊的光学性能,如强烈的旋光性,圆二色性和选择性反射光性能等;并带来相应的应用,正是由于高分子胆甾相材料的性能和应用,使得高分子胆甾相液晶的相态转变和结构变化也一直倍受关注。     

THE MORPHOLOGY AND STRUCTURE OF ETHYLCYANOETHYL CELLULOSE IN STYRENE AND POLYSTYRENE

Ethyl-cyanoethyl cellulose ((E-CE)C)/styrene solution could form anisotropic system when the concentration was high enough. The (E-CE)C/polystyrene(PS)multiphase polymer could be obtained by radical polymerization of the styrene in the solution. The (E-CE)C/PS multiphase polymer maintained both the crystalline structure of the (E-CE)C and the amorphous structure of the PS. In the multiphase polymer produced from the isotropic solution, however, the (E-CE)C formed spherulites and spread in the PS amorphous phase. While, in the multiphase polymer produced from the anisotropic solution, the (E-CE)formed cylinderic crystalline aggregates. Moreover, the ordered lamellar texture was also observed in the multiphase polymer produced from the anisotropic solution.     

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.     

UV irradiation gradient induced banded texture in photo-polymerized ethyl-cyanoethyl cellulose/poly(acrylic acid) cholesteric liquid crystalline films and patterns fabrication thereof

The photo-polymerization-induced banded texture of ethyl-cyanoethyl cellulose/acrylic acid/copper acrylate ((E-CE)C/AA/CuAA₂) cholesteric liquid crystalline (CLC) solutions were investigated. The results indicate that the CLC phase can be fixed by the photo-polymerization. Banded texture was obtained in the photo-polymerized CLC films. The orientation of the banded texture induced by the photo-polymerization depends on the gradient of UV irradiations on the surface of the (E-CE)C/AA/CuAA₂ CLC solutions. CLC films with different patterns can be obtained by introducing the UV irradiation gradient on the (E-CE)C/AA/CuAA₂ CLC solutions surface by using masks with different patterns. The simple approach for the fabrication of CLC films with different patterns may have the potential application in the fields of holographic image storage.     

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.     

Three-dimensional crystal alignment using a time-dependent elliptic magnetic field

A theoretical study has been presented to show that it is possible to align three different diamagnetic susceptibility axes (chi(3) < chi(2) < chi(1) < 0) of a crystallite with respect to the laboratory coordinate system (x, y, z). The time-dependent magnetic field that periodically changes in direction and intensity on the xy plane in an elliptic manner (the intensity stronger in the x direction) at a rate quicker than the intrinsic rate of magnetic response causes the three-dimensional alignment, that is, chi(1) parallel x, chi(2) parallel y, and chi(3) parallel z. The fluctuation of the three susceptibility axes around the corresponding laboratory coordinates is estimated in terms of the fluctuation around the minimum of the time-averaged magnetic potential. This technique enables the three-dimensional alignment of the crystallographic axes.     

Quiescent and strain-induced crystallization of poly(p-phenylene terephthalamide) from sulfuric acid solution

Quiescent and strain-induced crystallization of poly(p-phenylene terephthalamide) (PPTA) from sulfuric acid solution has been studied. Negative spherulites (SA-PPTA spherulites) are formed from hot concentrated solutions by cooling. The spherulite consists of radiating fibrous lamellae several hundred angstroms wide. The electron diffraction pattern indicates that PPTA molecules are oriented perpendicular to the long axes of the fibrous lamellae and that the [010] or [110] direction of the modification I crystal and [010] direction of the modification II crystal are parallel to the long axes of the fibrous lamellae. The width of the lamellae is much smaller than the chain length of the starting PPTA. It appears that hydrolysis of PPTA during melting crystallization determines the chain length, i.e., the width of the fibrous lamella. Stacked, lamellar structures like “row structures” are formed under shear. The longer axes of the fibrous lamellae are oriented perpendicular to the shear direction. It is confirmed by electron diffraction studies that the PPTA molecules are oriented parallel to the shear direction. Well-developed fibrils with the PPTA molecules oriented to the fibril axis, are formed by adding the SA-PPTA spherulites to water with vigorous stirring.     

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。     

Structure and magnetic properties of Co nanowires electrodeposited into the pores of anodic alumina membranes

Cobalt nanowires were obtained in the process of electrodeposition into pores of an alumina membrane. Structural research (XRD, TEM) of Co revealed the face-centered cubic structure. However, the existence of the hexagonal structure cannot be excluded due to strong texture. The influences of an external magnetic field and Al₂O₃ membrane geometry on magnetic properties of obtained wires were examined. It was found that cobalt nanowires exhibit pronounced shape anisotropy in a direction parallel to the wire axis. The highest influence on the magnetic properties is ascribed to the nanowires geometry i.e., height, diameter, and distances between single wires. Application of an external magnetic field in a perpendicular direction to the sample surface during cobalt electrodeposition increases magnetic anisotropy with a privileged direction along the wire axis. Application of the magnetic field in a parallel direction to the sample surface changes the direction of magnetization.     

PREPARATION AND PROPERTIES OF ETHYL-CYANOETHYL CELLULOSE/POLYACRYLIC ACID COMPOSITE FILMS WITH REFLECTION COLORS*

Ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid (AA) becomes a cholesteric liquid crystalline solution withvivid colors when the (E-CE)C concentration is 42 wt%～52 wt%. (E-CE)C/polyacrylic acid (PAA) composites withcholesteric structure were prepared by polymerzing AA in (E-CE)C/AA liquid crystalline solutions. The layers of orderedpolymer chains in the cholesteric phase were inclined during polymerization and the degree of the inclination depended onthe polymerization temperature and the concentration of the solution before polymerization. The cholesteric structure in thecomposites could not be changed when temperature was lower than 100℃. Cross-linking of the PAA in compositesimproved their water-resistance. The cholesteric order of the composites without cross-linking was destroyed when theywhere immersed in water. The color derived from the selective reflection of the cholesteric phase of the cross-linkedcomposites turned from blue to red after the composites absorbed water. The color of the composites could be returned to theoriginal one when the absorbed water was removed from the swollen composites.     

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。     

INFLUENCE OF THE SOLVENT SWELLING ON MACROMOLECULAR CHOLESTERIC LIQUID CRYSTALLINE STRUCTURE*

Ethyl-cyanoethyl cellulose [(E-CE)C]/cross-linked polyacrylic acid [PAA] molecular compositeswith cholesteric order were prepared. It was found that the macromolecular cholesteric structure was changedwith the swelling of PAA in the composites. The selective reflection of the cholesteric phase shifted to thelonger wavelength and the X-ray diffraction angle shifted to the high angle direction during swelling, whichsuggested that the cholesteric pitch and the number of the layers of ordered (E-CE)C chains in the cholestericphase were increased.     

Macromolecular cholesteric order observed by electron microscopy

The macromolecular cholesteric structure in the ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid [AA] cholesteric liquid crystalline solutions is studied by directly observing the morphology and structure of the ethyl-cyanoethyl cellulose [(E-CE)C]/polyacrylic acid [PAA] using electron microscopy. A periodical lamellar structure is observed in ultrathin slices of the composites with cholesteric order by both transmission electron microscopy (TEM) and low-voltage scanning electron microscopy (LVSEM). It is suggested that the periodical lamellar structure is induced by the twist of the molecular orientation in the cholesteric phase and reflects the structural features of the macromolecular cholesteric phase. The macromolecular cholesteric phase exhibits the twisted ring morphology in the initial stage of the formation of the liquid crystalline phase. The swelling of the ultrathin slices with cholesteric order in water is heterogeneous, which suggests the tight packing of the (E-CE)C chains in the direction of the helix axis in the macromolecular cholesteric phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 439–445, 1998     

原位磁场下粉末样品的X射线衍射图谱

To obtain more crystal and magnetic structural information of powder crystals,magnetic field is introduced into X'Pert-MPD XRD apparatus with the strength of 0. 42 T and two different directions:one direction of magnetic field is vertical to the sample holder and another is parallel. XRD patterns in situ magnetic field are obtained for six samples which are representative of paramagnetic,diamagnetic,ferromagnetic,ferrimagnetic,antiferromagnetic substances and reduction product of FeCl2 by NaBH4 respectively. Compared with XRD patterns obtained in the zero magnetic field,there are some diffraction peaks disappear,some occur,or some diffraction angles and counts change. In addition,the patterns are different under the different direction of magnetic field. The cause is that magnetic dipoles in crystals are oriented along with the direction of magnetic field. The oriented magnetic dipoles produce stress in crystals and make crystal lattice changed（such as magnetostriction）or even turn particles aligned along with the direction of magnetic field to form preferred orientation of particles.     

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.