Computational study of the texture formation in mesophase pitch‐based carbon fibres

This paper studies the thermal relaxation phenomena after melt‐extrusion of a rigid discotic uniaxial nematic mesophase pitch using mathematical modelling and computer simulation. The Ericksen and Landau–de Gennes continuum theories are used to investigate the structure development and texture formation across mesophase pitch‐based carbon fibres. The two‐dimensional model captures five types of transverse patterns, which match the commonly observed textures for mesophase pitch‐based carbon fibres. They are: random, zig‐zagged radial, radial, quasi‐onion and onion. These textures represent the various combinations possible from the interplay between structure (i.e. texture) development and cooling during the fibre spinning process. During the thermal relaxation after the cessation of extensional flow the discotic nematic molecules store elastic free energy decays. The distorted nematic molecular profiles reorient to release the stored elastic free energy. The difference in time scales for molecular reorientation and thermal relaxation result in different transverse textures. The rate at which the fibres are cooled is the main factor in controlling the structure development. A slow cooling rate would permit the nematic discotic molecules to reorient to a well‐developed (radial or onion) texture. The random texture is a result of rapid quenching. The numerical results are consistent with published experimental observations.     

Pattern formation and non-linear phenomena in stretched discotic liquid crystal fibres

This paper presents a non-linear numerical and bifurcation analysis of pattern formation phenomena in a discotic nematic liquid crystal confined to annular cylindrical cavities and subjected to extensional deformations. The results are of direct relevance to understanding the industrial melt spinning of mesophase carbon fibres, using discotic nematic liquid crystals precursor materials. Three types of orientation patterns are identified in this study: spatially constant (radial), monotonic (pinwheel), and oscillatory (zigzag). Numerical and closed form analytical results predicting continuous transformations between the radial, pinwheel, zigzag radial orientation modes are presented. The bifurcation analysis provides a direct characterization of the parametric dependence and the transitions between these three basic patterns, and provides a complete understanding of the multistability phenomena that is present in the oscillatory orientation patterns. In general it is found that small fibres of nearly elastically isotropic discotic nematic liquid crystals tend to adopt the classical ideal radial texture, while larger fibres with anisotropic elastic moduli tend to yield the zigzag texture. Fixed arbitrary surface orientation of intermediate size and anisotropy tend to adopt the pinwheel texture. The theoretical results are able to explain the main features and mechanisms that lead to the commonly observed cross-section textures of industrially spun mesophase carbon fibres.     

Texture dependence of capillary instabilities in nematic liquid crystalline fibres

Static and dynamic linear analyses of axisymmetric capillary instabilities in textured nematic liquid crystalline fibres are performed using the equations of nemato-statics and inviscid nemato-dynamics. Three representative textures, viz. axial, onion, and radial, are analysed to show all possible effects of Frank gradient elasticity on the wavelength selection and growth rate of peristaltic modes driven by surface area reduction. It is found that Frank elasticity may tend to stabilize or destabilize the fibre, depending on the initial fibre texture. Axial textures tend to stabilize the fibre through the director splay-bend distortions driven by surface tilting. Onion textures are destabilized by decreasing azimuthal bend elastic energy caused by surface displacement. Radial textures exhibit a stabilizing tilt mechanism due to bend modes and a destabilizing displacement mechanism due to splay modes, but the former is predicted to be dominant. The static analysis provides good estimates of the instability thresholds while the transient energy balance provides information on the fastest growing modes. The static and dynamic results are compared and shown to be fully consistent. The couplings between splay and/or bend distortions, surface tilting, and surface displacement in nematic fibres are characterized and used to explain the deviations from the classical Rayleigh instability.     

Simulation of texture formation processes in carbonaceous mesophase fibres

Carbon fibres are spun from carbonaceous mesophases using standard melt spinning techniques. These melt spun carbon fibres exhibit a set of distinct cross-sectional textures. Two widely reported textures in literature are the planar radial (PR) and planar polar (PP). This work uses a mesoscopic model, based on the classical Landau-de Gennes theory of liquid crystals adapted to carbonaceous mesophases, to elucidate the principles that control the texture formation processes. The model is able to capture the microstructure and the formation of the PR and PP textures. A phase diagram for classical PR and PP textures has been constructed in terms of temperature and fibre radius, thus establishing the processing conditions and geometric factors that lead to the selection of these textures. The multipath formation process of the planar polar texture through defect splitting, direct planar polar formation, and defect annihilation has been thoroughly characterized. The results of this work provide new knowledge for optimization and control of mesophase carbon fibre textures.     

Light-induced formation of curved needle texture by circularly polarized light irradiation on a discotic liquid crystal containing a racemic chromium complex

We have found that the discotic nematic liquid crystal, hexakis(4-nonylphenylethynyl)benzene (HNEB), doped with the racemic chromium complex Cr(Ocacac)₃, shows a novel straight-needle texture with hexagonal columnar alignments, changing to a curved-needle texture under irradiation of circularly polarized light (CPL). This novel phenomenon is specific to the mixture of HNEB and Cr(Ocacac)₃. The formation of curved needles means that chiroselective photoinversion of racemic Cr(Ocacac)₃ by CPL irradiation induces a needle direction change in a discotic liquid crystal. The change in chirality of Cr(Ocacac)₃ in HNEB induced by CPL irradiation, and the resulting nano-segregation of its enantiomers during cooling from the isotropic to mesophase of HNEB, are considered to influence changes in the alignment of columns and/or small domains of column aggregates in the discotic liquid crystal.     

Bifurcational analysis of the isotropic-discotic nematic phase transition in the presence of extensional flow

A bifurcational analysis is performed on a version of Doi's equation of nematodynamics that describes the non-equilibrium isotropic-discotic nematic phase transition in the presence of steady uniaxial extensional flow. The disc-like molecular geometry and the degenerate extensional flow-induced orientation are shown to be the source of a complex bifurcation and multistability behaviour involving two physically equivalent biaxial nematic phases, one uniaxial nematic phase and one uniaxial paranematic phase. Depending on the temperature and the extension rate, the isotropic-discotic nematic transition, involving the two biaxial nematic phases and the uniaxial paranematic phase, may be continuous (2nd order), discontinuous (1st order), or it may exhibit a tricritical non-equilibrium phase transition point. A validation procedure on the validity of the predictions is implemented. The predictions presented here find practical applications in the industrial spinning of mesophase carbon fibres, and also provide new results that increase the present fundamental understanding of the rheology of discotic nematic liquid crystals.     

Synthesis and mesomorphic behaviour of novel chiral nematic side chain liquid crystalline polysiloxanes

A series of novel thermotropic side chain liquid crystalline polymers was synthesized by grafting copolymerization of a mesogenic monomer, 4-allyloxybenzoyl-4′?-(4-n-alkylbenzoyl)–p-benzenediol bisate and a chiral monomer, menthyl undecylenate. The mesogenic monomers exhibited nematic threadlike textures during heating and cooling. The polymers showed thermotropic liquid crystalline properties with a broad mesomorphic region over a range of 100°C. The polymers exhibited a cholesteric mesophase with a colourful Grand-Jean texture when the content of chiral units was greater than 15?mol?%; the others exhibited nematic threadlike textures. All of the polymers were thermally stable over 300°C, and most were laevorotatory as the chiral monomer.     

Chiral symmetry-breaking dynamics in the phase transformation of nematic droplets

Dynamic simulations of the isotropic–nematic phase transformation of liquid crystal droplets with homeotropic surface anchoring are found to predict chiral symmetry-breaking dynamics. These observations occur when using material parameters for pentyl-cyanobiphenyl (5CB) but not with the single elastic constant approximation for this material, which is frequently used in simulations. The twisting dynamic process occurs during the relaxation of the domain from an unstable radial texture to a stable uniform texture and involves simultaneous defect loop motion and twisting of the bulk nematic texture.     

Anchoring properties of a lyotropic,nematic discotic CsPFO/water mixture

Abstract

A sample of a CsPFO/water mixture in the nematic discotic phase is used to investigate liquid crystal anchoring properties. A splay distortion is introduced in the uniform nematic alignment and orientation and relaxation processes are observed. From experimental values of the orientation and relaxation times we determine the rotational viscosity and the splay elastic constant for this mixture.     

Pentaerythritol Derived Tetrapode Exhibiting a Nematic-Like Mesophase at Ambient Temperatures

The nematic liquid-crystalline phase exhibits average orientational order, with no positional organisation. So-called modulated nematic phases exhibit this same orientational order with an additional spatially periodic modulation of the nematic director, the most common of which is the twist-bend nematic phase. We report a pentaerythritol derived tetrapode which exhibits a nematic-like mesophase at ambient temperature, and we denote this new mesophase ‘N_X’ to indicate a nematic phase of unknown structure. X-ray scattering experiments refute the possibility of positional order, yet optical textures are consistent with a periodic structure. We suggest that the mesophase exhibited by this material is a new type of nematic-like mesophase with some form of modulated structure. We find the N_X phase to exhibit an electrooptic response consistent with a nematic-like phase.     

Experimental studies on the phase diagram and physical properties of mixture of calamitic and discotic nematic liquid crystals

Physical studies on mixture of calamitic and discotic nematic liquid crystals are meagre although they are potential for optimising physical properties. Here, we report experimental studies on the phase diagram and physical properties of mixtures of ambient temperature discotic and calamitic nematic liquid crystals. A substantial decrease in several physical properties such as birefringence, dielectric anisotropy and elastic constants are observed with increasing wt% of discotic compound. On the other hand a large increase in the rotational viscosity is observed. Based on the experimental results a simple model of mutual orientation of the rod-like and disc-like molecules is proposed.     

Prediction of Nematic Mesomorphism. Compounds with Disclike Molecules

Molecular parameters for 136 compounds with disclike molecules and known phase diagrams were calculated and analyzed by a procedure proposed previously in order to improve the method for predicting possible types of mesomorphism from molecular characteristics. A correlation between the value of the molecular parameter M _m and the existence of a nematic liquid crystal is established. An analysis of calculated values of M _m for 27 new molecules of similar structure yielded compounds that are likely to form nematic liquid crystals. To verify the prediction, one of these compounds — 1,3,5cyclohexanebenzoatebenzene — was synthesized and its phase diagram was studied. The prediction results agree with experimental data: the range of existence of a nematic mesophase was established (130.5–134.5°). Rapid cooling followed by prolonged storage of samples at room temperature without mechanical deformation led to vitrification of the samples ith preserved mesophase texture. Mechanical deformation of vitrified samples resulted in their transition to the crystal phase.     

Peculiarities of the phase behavior of 1,3,3′,5,5′-alkoxybenzoate biphenyls in mixtures with chiral and discotic mesogenes

A synthesis of 1,3,3′,5,5′-alkanoyloxy-(Ia) and 1,3,3′,5,5′-alkoxybenzoate biphenyls (Ib) has been performed. Peculiarities of phase behavior of liquid crystalline 1,3,3′,5,5′-alkoxybenzoate biphenyls (Ib) in mixtures with discotic (1-nitro-2,3,6,7,10,11-hexadecyloxytriphenylene — II and triphenylene 2,3,6,7,10, 11-hexaundecyloxybenzoate — III) and chiral (cholesterol undecylate — IV) were studied with the aim of identifying the type of mesomorphysm. Ib was found to be mutually soluble with II and III and partially soluble with IV. The construction and analysis of the phase diagram of the mixtures of I with II throughout the range of concentrations makes it possible to assign the studied biphenyl Ib to discotic mesogens. An area of the smectic phase, which is formed from the chiral nematic IV and the discotic mesogen Ib (which displays dimorphism in the mesophase) have been found for the first time in the mixtures of these compounds. During cooling, in the mixture with molar ratio 1:1 dendritic textures with grained branches are formed, which are similar to those described in literature for TGB (twist grain boundary) phases. Relying on our studies, we suggest that Ib has a columnar type of the structure in the low-temperature area and a nematic, probably chiral, type in the high-temperature area of the mesophase.     

Nematic phase transition and texture dynamics

ABSTRACT

Research advances over the past decade in the areas of nematic phase transition and texture dynamics are reviewed. Research studies applying theoretical techniques able to resolve the length and time scales inherent to liquid crystal (LC) dynamics are focused on: coarse-grained molecular dynamics and continuum mechanics. The focus on LC dynamics is due to their importance in both fundamental and technological processes involving complex LC textures and texture transitions. Meta-stable textures frequently occur in soft matter systems, thus knowledge of LC textures that result in free energy minima for a specific system is not sufficient to characterise its behaviour. Resolution of dynamics enables researchers to predict with more accuracy observable LC textures and texture transitions. As is reflected in the reviewed research, LC dynamics simulations have enabled both validation of simulations with existing experimental observations and predictive results, which augment direct experimentation. While the outlook is positive as a result of this, several key challenges stymie further progress: (i) the availability of validated open-source software implementing nematic dynamics simulation methods, (ii) development of suitable visualisation and characterisation methods for transient three-dimensional LC textures, and (iii) inclusion of thermal fluctuations in nematic dynamics models.     

Structure of liquid crystal droplets with chiral propeller texture

We experimentally studied a nematic liquid crystal whose molecules form twisted head-to-head H-bonded dimers. We observed that when the material transformed from the isotropic to nematic phase, it formed droplets with chiral propeller textures. We carried out a computer simulation to investigate the liquid crystal director configuration inside the droplets and to study the effects of elastic constants and chirality on the droplet texture. Results of our study show it is likely that the material in the droplets had nonzero chirality due to spontaneous chiral phase separation.     

Ringlike cores of cylindrically confined nematic point defects

Nematic liquid crystals confined in a cylindrical capillary and subjected to strong homeotropic anchoring conditions is a long-studied fundamental problem that uniquely incorporates nonlinearity, topological stability, defects, and texture physics. The observed and predicted textures that continue to be investigated include escape radial, radial with a line defect, planar polar with two line defects, and periodic array of point defects. This paper presents theory and multiscale simulations of global and fine scale textures of nematic point defects, based on the Landau-de Gennes tensor order parameter equations. The aim of this paper is to further investigate the ringlike nature of point defect cores and its importance on texture transformation mechanisms and stability. The paper shows that the ringlike cores can be oriented either along the cylinder axis or along the radial direction. Axial rings can partially expand but are constrained by the capillary sidewalls. Radial rings can deform into elliptical structures whose major axis is along the capillary axis. The transformation between several families of textures under capillary confinement as well as their stability is discussed in terms of defect ring distortions. A unified view of nematic textures found in the cylindrical cavities is provided.     

New inductions of columnar mesophases in nematic discotic multiyne mesogens [1]

In examples of two large naphthalene- and triphenylene-centred hexaynes exhibiting only the nematic discotic (N_D) type of mesophase, a new kind of phase induction was observed. These disc-shaped nematogens were doped with numerous dipolar carbocyclic compounds leading to the induction of two types of columnar mesophase (i.e. D_ro and D_ho). The phase behaviour of these binary systems, depending on the structure of the dopant applied, was studied by polarizing microscopy.     

Electrooptical properties of mesogenic chain molecules in solution and in nematic state

Electrooptical characteristics of mesogenic chain molecules in solution and in mesophase can be described in terms of intra- and intermolecular orientational orders. The value and sign of electric birefringence δn in a solution of kinetically rigid chain molecules are determined by the combination of two factors: intramolecular orientational order which depends on the dipolar and anisotropic architecture of the molecule and intermolecular orientational order caused by the action of the external electric field E. The value and sign of the dielectric anisotropy δε of the polymer nematic phase are also determined by the combination of intra- and intermolecular orders. However, in this case the latter is not maintained by the external field but by the nematic potential of the mesophase. Therefore, comparative investigations of electrooptical properties of polymers in solutions and in nematic melts make it possible to obtain information about the intra- and intermolecular orientational orders of the molecules under investigation in these two states. These investigations were carried out using the method of electric birefringence in solutions and the method of orientational deformations of nematic textures in an electric field. The objects being investigated were nematogenic dimers and trimers. Experimental data obtained for these compounds showed the presence of intramolecular order in their molecules, which is manifested in the odd-even oscillations of the value and sign of Kerr constant K≈δn/E² in solution and δε in the nematic phase when the number of C-C bonds in the methylene spacers of these molecules is varied. This effect is particularly dramatic in the mesophase where it is enhanced by intermolecular nematic potential.     

Non-symmetrical discotic liquid crystalline dimers: molecular design,synthesis and mesomorphic properties‡

The synthesis and mesomorphic properties of novel non-symmetrical discotic dimers have been investigated. Dimers have been prepared by the combination of electron-deficient (n-type) anthraquinone and electron-rich (p-type) triphenylene discotic monomers. The mesophases have been characterised using polarising optical microscopy, differential scanning calorimetry and X-ray diffraction. Most of the dimers have been shown to exhibit a rectangular columnar mesophase and one has a nematic columnar mesophase also. Charge transfer behaviour has been studied by UV–Vis spectroscopy.     

Structural and dynamic properties of a new type of discotic nematic compounds

Thermodynamic, structural and dynamical properties of a new type of discotic compounds, a hydrocarbon without any heteroatoms, displaying a nematic discotic phase have been investigated by means of X-ray diffraction, electro-optical relaxation, and calorimetric studies. Of particular interest are the strength of the first order nematic—isotropic phase transition and the nature of the orientational fluctuations in the isotropic phase. The short range positional order was found to be biaxial in both the isotropic and the nematic phase. The isotropic phase displays strong pretransitional effects originating from orientational fluctuations in the neighbourhood of the transition to the nematic phase. The character of these pretransitional effects differs from that found for calamitic systems in that the number of correlated molecules g₂ is extremely large, of the order of 600 at the clearing temperature and the electro-optical relaxation time is very large, caused by the large value of g₂.