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.     

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.     

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.     

Thermal transition of a wholly aromatic thermotropic liquid crystalline copolyester

A copolyester was prepared from p-hydroxybenzoic acid (HBA), 2,6-naphthalene dicaboxylic acid (NDA), and hydroquinone (HQ). Thermal transition behavior and the crystal structure of this copolyester were investigated by using polarized light microscopy (PLM), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WAXD) after annealing at solid-phase polymerization conditions. A glass transition or newly ordered structure in the 270–290°C range was observed on annealing at 260°C, which increased with annealing time, attributed to mobility and reactive rearrangement in amorphous regions. Broad and unclear WAXD profiles and multimelting behaviors were found on annealing at 280°C, and explained by hexagonal and orthorhombic lattice formation and transformation. A large increase in melting temperature was observed only on annealing at a temperature (320°C) near the crystal–nematic transition, suggesting annealing temperatures near the melting point are required for sufficient mobility to afford crystalline rearrangement via transesterification. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3763–3769, 1999     

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.     

Banded texture in sheared a semiflexible thermotropic liquid-crystalline polyester and its graft copolymers with polyolefins

The formation of banded texture both in a semiflexible thermotropic liquid-crystalline polyester (SBH 112, synthesized from sebacic acid, 4,4′-dihydroxybiphenyl and 4-hydroxybenzoic acid, from Eniricerche, Milan) and in a blend of SBH with graft copolymers, consisting of a polyolefin (polyethylene or polypropylene) backbone and SBH grafts (COPPE, COPPP) has been studied by polarization microscopy and by scanning electron microscopy. The influence of the preparation conditions upon the perfection, characteristics and thermal stability of the banded texture has been investigated. The results show that the banded texture formed in SBH sheared films possesses greater perfection, smaller band width and larger angle of deviation, and higher thermal stability than the banded texture formed in COPPE and COPPP prepared under similar conditions. It has been assumed that the chain rigidity of the macromolecules of the system is mainly responsible for the formation and perfection of the banded texture. Received: 17 March 2000 Accepted: 26 July 2000     

Non-equilibrium thermal behaviour of a main chain thermotropic polymer

Abstract

The effect of thermal treatment on the thermodynamic properties and structure of a nematic thermotropic main chain polymer with mesogenic groups containing 3,3′-biphenylene units and octamethylene flexible spacers (BF8) has been studied by DSC and X-ray scattering. We have found that BF8 samples do not crystallize even on very slow cooling from the isotropic state, and possessed a glassy nematic structure at room temperature. The strong influence of the cooling rate on both the enthalpy of the nematic-isotropic transition and the rise of specific heat at the glass transition for BF8 samples was observed. It was attempted to explain this result in terms of the improvement of the nematic structure during cooling.     

Non-equilibrium thermal behaviour of a main chain thermotropic polymer

The effect of thermal treatment on the thermodynamic properties and structure of a nematic thermotropic main chain polymer with mesogenic groups containing 3,3'-biphenylene units and octamethylene flexible spacers (BF8) has been studied by DSC and X-ray scattering. We have found that BF8 samples do not crystallize even on very slow cooling from the isotropic state, and possessed a glassy nematic structure at room temperature. The strong influence of the cooling rate on both the enthalpy of the nematic-isotropic transition and the rise of specific heat at the glass transition for BF8 samples was observed. It was attempted to explain this result in terms of the improvement of the nematic structure during cooling.     

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.     

Deorientation effects on extrusion rheometry of a thermotropic copolyester

Extrusion rheometry experiments with a commercial thermotropic liquid crystalline copolyester show concave Bagley plots and convex pressure profiles. A loss of the orientation produced at the entrance of the capillary and the slit can explain these non-linearities. Assuming that the order parameter, S, relaxes exponentially with time, the Doi-Edwards model for the shear flow of rod-like polymers is used to adjust experimental data.     

Crystallization and melting behavior of a main-chain thermotropic copolyester

The crystallization and melting behavior of a main-chain thermotropic copolyester has been investigated by differential scanning calormetry (DSC). The effect of annealing time and temperature on the transition temperatures and enthalpies has been evidenced. Two melting peaks are observed and the first one clearly develops on annealing. Hypotheses are suggested about the crystallization mechanism.     

The identification of the sign and strength of disclinations in the schlieren (nucleated domain) texture of the nematic phase,by optical microscopy

ABSTRACT

The optical texture of the nematic phase, variously known as the schlieren, structure à noyuax or nucleated domain texture, was identified over a century ago as being an array of point singularities. When viewed between crossed polars, patterns of dark brushes radiate from each point nucleus. The sign and strength of each nucleus can be uniquely determined from the changes in the orientation of these brushes when either the sample or the crossed polars are rotated, from two formulae given by Chadrasekhar in 1977. However, these were given with little exemplification and have been largely overlooked. Consequently, the majority of the discussions given in current literature are either incomplete and confusing or, in some cases, incorrect. Here, we provide a detailed explanation of the textures and their behaviour as viewed with the most commonly used experimental geometry (i.e. with a rotating sample and stationary polars).     

Investigations on aromatic polyesters with polynaphthalene systems in the main chain—X. Studies on the determination of chemical inhomogeneity of aromatic copolyester chains

The turbidimetric titration technique was applied to determine, for a number of solvent-nonsolvent systems, the relation between the parameter $\text{γ}{}^1$ and the content of 2,2 bis(4-hydroxyphenyl) propane in the terephthalic copolyester of 4,4′ dihydroxydinaphthyl 1,1′ and 2,2 bis(4-hydroxyphenyl) propane. A system most sensitive to differences in the chemical composition of the copolyester was found and then used to fractionate two copolyesters obtained in different reaction conditions and having the same composition but differing in the arrangement of comonomer units in the chain. Fractionation results have been presented in the form of MWD curves and also as a relation between the content of 2,2 bis(4-hydroxyphenyl) propane and the intrinsic viscosity [η] of individual fractions.     

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     

Super structure formation in a wholly aromatic copolyester fiber

The structure of a wholly aromatic copolyester fiber containing 60 mol% p‐hydroxybenzoic acid (PHB), 20 mol% 4−4′‐dihydroxydiphenyl, 15 mol% terephthalic acid and 5 mol% isophthalic acid was studied by means of electron microscopy and wide‐angle X‐ray diffraction. The X‐ray diffraction pattern of the wholly aromatic copolyester fibers showed two sets of diffractions: one set was composed of sharp spots which arose from relatively high crystalline phase. The crystal structure analyzed by these spots was orthorhombic and the lattice dimensions were a = 0.869 nm, b = 0.510 nm, c = 1.20 nm and ρ = 1.50 g/cm³. Another set was characteristic of streaks on the meridian extending parallel to the equator. X‐ray scattering intensity distribution on the meridian was calculated as the square of Fourier transform of random chain model. Comparison of this intensity distribution with the observed meridional maxima concluded that the streaks were due to rather disordered chains with a PHB content of less than 50%. Dark field image (DFI) taken from the meridional 002 reflection showed that slender crystallites were distributed over the whole visual field, oriented parallel to the fiber axis. On DFI from the equatorial 200 reflection, some of these crystallites were also observable, forming groups that distributed randomly in the field. All crystallites belonging to the same group co‐oriented in a*‐ and c*‐axis directions, though disordered parts intervened among the crystallites. This is attributed to the fact that, though the content of PHB in the segments of disordered parts was only 50%, these PHB held the co‐orientation among the slender crystallites within one group. Heat treatment induced the development of block segment and subsequent crystallite growth with fiber. This reorganization improved the thermostability and the mechanical properties. Copyright © 2000 John Wiley & Sons, Ltd.     

Nanostructure reorganization in a thermotropic copolyester. A simultaneous WAXS and SAXS study

Thermally induced Angstrom and nanometer‐scale reorganization in thermotropic liquid crystalline polymer based on (1,4)‐hydroxybenzoic acid (B) and (2,6)‐hydroxynaphthoic acid (N) was investigated by simultaneous wide‐angle and small‐angle X‐ray scattering (SAXS, respectively). Extruded tapes 50 µm thick were annealed at 240°C under dry air conditions. The as‐received tape exhibited fiber‐like structure with crystalline order, whereas the SAXS patterns exhibited diamond‐shaped diffuse scattering elongated along the equatorial axis elucidating nanovoid morphology oriented along the extrusion axis. Guinier analyses showed that the radius of gyration R_g of nanovoids were ca. 17 nm along the extrusion axis. Heat treatment produced a sharpening of the 002 meridional reflection and the 110 equatorial reflection suggesting an improvement of molecular register and packing. The molecular alignment, as quantified by the order parameter , increased as well as the degree of crystallinity χ. On the other hand, SAXS intensity along the equatorial axis decreased evidencing reduction of R_g, i.e. lateral compression of the nanovoids and better molecular packing. Thermal treatment increased the thermal stability and the uniaxial tensile Young's modulus, E, along extrusion axis. However, the tapes exhibited microhardness anisotropy and the indentation anisotropy, ?H, gradually decreased suggesting reduction of elastic recovery in the molecular chain direction. Scanning electron microscopy evidenced an outer skin with an internal layered morphology that transformed into sheet‐like morphology with meandering fibrils. This investigation evidenced microstructure and morphology reorganization correlating with improved thermal and mechanical properties. Copyright © 2015 John Wiley & Sons, Ltd.     

Measurement of the interfacial tension between polyethersulfone and a thermotropic liquid-crystalline copolyester

Due to the increasing interest in forming blends of liquid-crystalline polymers with conventional thermoplastics, it becomes important to determine the interfacial tension between two such polymers. A method for evaluating the interfacial tension between a thermotropic copolyester based on hydroxybenzoic and hydroxynaphthoic acid residues, and polyethersulfone is presented, based on the Fort and Patterson method. It is found that the value of the interfacial tension in the melt is much higher than is the case between conventional polymer pairs. It is suggested that this high value reflects an entropic effect due to the strong exclusion of the flexible coil polymer from the nematic melt. © 1993 John Wiley & Sons, Inc.