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.     

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 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.     

Crystalline morphology of a thermotropic aromatic polyester crystallized from nematic melt

The crystalline morphology of a thermotropic aromatic polyester crystallized from a nematic melt was investigtated by means of polarized optical microscopy (POM) and scanning electron microscopy (SEM). Due to POM measurements it was found that spherulites of two different types are formed within the two different temperature regions. When T_c was exceeding 170°C, spherulites of type‐1 showing a negative birefringence grew with a radial fibrillar morphology and exhibited a clear Maltese‐cross pattern. The radius growth rate of type‐1 spherulites was about 2.2 μm/min at 185°C. When T_c was smaller than 160°C, spherulites of type‐2 were formed and exhibited a radially outward growing structure but no evident Maltese‐cross pattern. These spherulites could be seen by the naked eyes due to their size reaching several millimeters. SEM observations revealed that the spherulites of type‐1 exhibited a ripple‐like homocentric morphology with periodical compact fibrils having a diameter of about 150 nm perpendicular to the radial direction. In contrast, the spherulites of type‐2 exhibited, as apparent from performed SEM images, radially growing crystallites of about 500 nm in size with no periodicity in the radial direction.     

Director fields of disclinations in the nematic mesophase decorated by focal‐conic texture for side‐chain liquid crystalline polymers

A new decoration method termed as focal‐conic texture decoration has been established to map the director field of disclinations of nematic mesophases for a side‐chain liquid crystalline polymer (SCLCP) based on its transition from nematic to smectic phase with focal‐conic texture observed under a polarizing optical microscope. FT‐IR microscopy was used to ascertain the relationship between the mesogenic orientation direction and the orientation direction of focal‐conic texture, which exhibits consequently the director field of a disclination.     

Rheology of a thermotropic polyester in the nematic and isotropic states

The rheological properties of a thermotropic polyester were determined in the nematic and isotropic states. In the isotropic state, the viscosity is almost constant and the polymer is only slightly elastic. The nematic phase has a lower viscosity than the isotropic, except at low frequencies or shear rates, where the viscosity increases as though the polymer had a yield stress. There is a marked dependence of the rheology on shear history. The effects of shearing can be erased by returning the material first to the isotropic state and then back to the nematic state. The results are discussed with reference to analogous observations in small-molecule liquid crystals and in thermotropic aromatic co-polyesters.     

Recent advances in the observation of disclinations of main-chain nematic polymers

Experimental observation of disclinations of main-chain nematic polymers is reviewed. The geometry of disclination structure is discussed both from observations of schlieren texture and the theory of curvature elasticity for a two-dimensional case with equal splay and bend moduli. The effects of non-equal elastic moduli, the nature of the disclination core and the observation of inversion wails are briefly mentioned. Examples of experimental observation of disclinations of high topological strengths up to S=4 are given. The main experimental methods to map the director field around disclinations are 1) lamellar decoration, 2) band-texture decoration and 3) surface microcrack decoration. The methods are discussed and compared, and examples illustrated by electron micrographs or photomicrographs are presented.     

Relationship between the Frank elastic constant anisotropy measured from the lamellar director and that of the molecular director around disclinations in main chain liquid crystalline polymers

Abstract

The transmission electron microscope technique enables direct visualization of disclination core structure of main chain liquid crystalline polymers. Generally, the lamellar structure, that is a function of type of polymer and molecular length, and of which the thickness is 10–200 nm, can be observed. In terms of distortions in the director field produced by a disclination, the elastic anisotropy, ?, can easily be calculated. However, the ? does not indicate the molecular distortion produced by the disclination. Continuum mechanics is used to describe the relationship between the elastic anisotropy, ?_a, measured from the lamellar director and that, ?_b, of the molecular director in main chain liquid crystalline polymers. The relationship is ?_a = ??_b, indicating that lamellar distortion is completely different from the molecular distortion.     

Relationship between the Frank elastic constant anisotropy measured from the lamellar director and that of the molecular director around disclinations in main chain liquid crystalline polymers

The transmission electron microscope technique enables direct visualization of disclination core structure of main chain liquid crystalline polymers. Generally, the lamellar structure, that is a function of type of polymer and molecular length, and of which the thickness is 10-200 nm, can be observed. In terms of distortions in the director field produced by a disclination, the elastic anisotropy, ε, can easily be calculated. However, the ε does not indicate the molecular distortion produced by the disclination. Continuum mechanics is used to describe the relationship between the elastic anisotropy, ε_a, measured from the lamellar director and that, ε_b, of the molecular director in main chain liquid crystalline polymers. The relationship is ε_a = -ε_b, indicating that lamellar distortion is completely different from the molecular distortion.     

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.     

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.     

EPR study of free radicals in a main chain thermotropic polymer

Free radicals were generated in a rigid rod-like copolymer via mechanical route and by gamma radiation. The (EPR) method was used for studying free radicals formed at 123 K. The spectra of free radicals observed and the influence of molecular motions on the transport of radical centers in the fracture surface layer are discussed.     

Modelling of director equilibrium states in a nematic cell with relief surface

We study two-dimensional equilibrium configurations of nematic liquid crystal (NLC) director in a cell bounded by two parallel surfaces. One surface is planar and the other one is spatially modulated. The relief of the modulated surface is described by a smooth periodic sine-like function. The orientation of NLC director easy axis is assumed to be homeotropic at one cell surface and planar at the other one. The NLC director anchoring with cell surfaces is assumed to be strong. We consider the case where disclination lines occur in the bulk of NLC above the extrema of the modulated surface. These disclination lines run along the crests and troughs of the surface relief. If the orientation of director at both bounding surfaces is of the same type, then NLC director field is continuous. For both configurations mentioned above (with defects and without defects), we obtain analytical expressions for director distribution in the bulk of NLC in the approximation of planar director deformations. Equilibrium distances from disclination lines to the spatially modulated surface are calculated when the defects occur. The dependences of these equilibrium distances on the period and depth of surface relief and the cell thickness are investigated in detail.     

Photoinduced gliding of the surface director in azo-dye doped nematic liquid crystals

We report photoinduced surface director gliding with azo dye-doped nematic liquid crystals. This gliding has the same characteristics as that induced by an applied magnetic field. Fast and slow dynamic regimes are observed, the latter fitting to a stretched exponential. In addition, the gliding demonstrates a 'sensitizing' effect for sequential measurements.     

Studies of the thermotropic mesophase behaviour exhibited by a highly asymmetric tetrabenzotriazaporphyrin derivative

The thermotropic mesophase behaviour of an asymmetrically shaped and highly substituted tetrabenzotriazaporphyrin (TBTAP) derivative has been studied by optical microscopy, DSC and X-ray diffraction. The TBTAP macrocycle differs from the more common phthalocyanine ring system by the substitution of a methine for a nitrogen at one meso-position. The TBTAP core was substituted with a single heptadecyl chain at this meso-position and four neopentyl groups were statistically distributed around the peripheral benzene rings. In contrast to an earlier study of this system which described the structure of the mesophase as discotic lamellar, detailed X-ray diffraction study indicates that the TBTAP derivative forms a disordered hexagonal columnar mesophase (Col hd ), with a weak tendency towards antiparallel orientation of neighbouring molecules observed in the form of a weak pseudo-centred rectangular packing.     

The alignment of cybotactic groups in a nematic mesophase by an electric field

The anomalous electric field alignment of the nematic mesophase of 4,4′-dimethoxyazoxybenzene, as inferred from the electron resonance spectrum of dissolved vanadyl acetyl acetonate, is discussed. A model, based on the alignment of cybotactic groups with their planes parallel to the electric field, is able to account for the major features of the angular dependence of the spectrum. The analysis shows that, at 125°C, the molecular axes are inclined at least 13° to the plane of the cybotactic group.