Simulation of transient banded textures of sheared nematic polymers

Nematic polymers, under certain conditions, develop a transient banded texture after cessation of simple shear flow when observing the sheared sample between crossed polars. Here we present a viscoelastic model that describes the formation mechanism of this well-characterized but yet unexplained phenomenon for a typical uniaxial rigid rod nematic polymer. It predicts that the relaxation of shear-flow enhanced scalar order parameter spatial fluctuations produces spatially periodic torques on the director, thereby producing a transient banded texture when viewing the sample between crossed polars. Our numerical results and digitized optical pattern are in good agreement with reported experimental observations.     

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).     

The parabolic focal conic texture in a lyotropic liquid-crystalline polymer

Hydroxypropyl cellulose (HPC) forms liquid-crystalline solutions in both water and methanol. When these solutions are sheared, the banded texture seen in many liquid-crystalline polymers is formed. Detailed optical microscopy of the bands has been carried out, showing that the bands arise from a smooth variation in the orientation of the local extinction directions, and not (as previously suggested in the literature) from sharp kinks. Over a period of time, the bands degenerate to form a new texture, which appears as a square grid pattern of extinction when specimens are viewed between crossed polars. The location of the corners of the squares depends on whether the microscope is focused near the top or bottom surface. When focus is altered to the middle of the sample, the periodicity of the pattern is halved. This texture is identified with the parabolic focal conies previously seen in small molecule smectic and cholesteric materials.     

A study on the relaxation phenomena of nematic polymers after cessation of shear flow

A viscoelastic model, composed of the Ericksen and Landau-de Gennes nematic continuum theories, is used to study numerically the relaxation phenomena after cessation of simple shear flow for a model rigid rod uniaxial nematic polymer. This model predicts that under certain conditions the relaxation of stored molecular and coupling elastic free energies due to periodic fluctuations in the scalar order parameter results in a transient periodic distortion of the director field. These conditions are that: (1) the ratio of the wavelength scales of the initial periodic spatial variation in the scalar order parameter k_s to the initial periodic planar director orientation fluctuation kφ (i.e. k_S/kφ) and the amplitude of the initial S spatial variation exceed certain minimum values, and (2) kφ is not zero. It is shown that the wavelength selection mechanism is controlled by the director reorientation-induced backflows. The digitized optical patterns of the transient periodic director field show transient periodic optical patterns similar to the transient banded texture nematic polymers exhibit after cessation of shear flow when observed between crossed polars. The numerical results and digitized optical patterns replicate frequently reported experimental observations.     

Effect of the thermal history on the phase transition and the liquid crystalline structure of thermotropic polyesters

A series of triad type thermotropic polyesters based on phenylsulfonyl hydroquinone and α,ω-bis(4-carboxyphenoxy)alkane was prepared, and the effect of the thermal history on the phase transition and the liquid crystalline structure of the polyesters was studied. The phase transition was significantly affected by the thermal history. When annealed at various temperatures, multiple endotherms were observed for all polyesters in DSC thermograms. A phase stability concept was employed to explain the complicated phase transitions. The time evolution of the liquid crystalline structure was investigated by optical microscopy and transmitted light intensity measurement under crossed polars during annealing. The steady decrease in the density of disclinations with accompanying increase of transmitted light intensity was observed. Depending on the surface conditions of the liquid crystal polymer film, two markedly different domain growth patterns and different textures were found on isothermal annealing; the continuous wormlike texture and the discontinuous droplet texture. The structural relaxation of the deformed texture during annealing was also studied. When shear was applied, the characteristic banded texture was formed in all polyesters.     

Crystallization and morphology of melt-solidified poly(vinylidene fluoride)

Crystallization of poly(vinylidene fluoride) (PVF₂) from the melt yields two types of spherulites. The first consists of large, highly birefringent, and tightly banded spherulites of the α-form, which are seen at all temperatures. The second type, termed mixed, crystallizes with a newly reported unit cell which appears to be the correct one for γ-PVF₂, but may contain inclusions of a different form (probably α-PVF₂); it is seen only at relatively high temperatures and frequently exhibits irregular or disorganized birefringent and morphological features. In thin films, some mixed spherulites contain regions of single-crystal-like aggregates which are grown parallel to the substrate and appear essentially nonbirefringent between crossed polars. Mixed spherulites frequently undergo transformations at their growth fronts leading to initiation of α-growth. These transformations are associated with the generally higher growth rate of α-spherulites which may exceed that of their mixed counterparts by almost seven times. However, with increasing temperature this difference in growth rates is progressively reduced and ultimately reversed.     

BANDED TEXTURE FORMATION IN NEMATIC SOLUTION OF POLY (1,4-BENZAMIDE) IN SULFURIC ACID

The banded texture in films prepared from nematic poly (1,4-benzamide) (PBA)/H_2SO_4 solution by shearing and without shearing has been studied by using microscopy techniques. The kinetic parameters of banded texture formation γ_c and τ_b were measured for nematic solution of PBA by using parallel-plate shearing apparatus. The banded texture was also observed in randomly packed domains for nematic solution of PBA on standing without shearing. The properties of banded texture show no difference between the two samples with or without shearing.     

Analysis of transient periodic textures in nematic polymers

A numerical solution of the Leslie-Ericksen equations for nematic liquid crystals is obtained for in-plane rotation of a strong magnetic field. A transient periodic orientation develops as a result of in-plane director motion and the induced shear flow. At long times the in-plane director orientation results in steady splay-bend inversion walls. A linear stability analysis shows that the inversion walls are unstable to perturbations out of the plane for elastic coefficients characteristic of nematic polymers. Calculations of transmitted light intensity through crossed polarizers for the computed orientation development predict the evolution of a banded texture, as observed experimentally.     

Structure development of fibers from liquid-crystalline PET/60PHB copolyester

Effect of extrusion conditions, particularly temperature, on the structure development of fibers from poly(ethylene terephthalate) modified with 60 mol% p-hydroxybenzoic acid was investigated. Light microscopy revealed that the structure of the liquid-crystalline fiber was highly dependent on the extrusion temperature: low-temperature-spun fibers exhibited a structure with domains or clusters of crystallites randomly oriented, whereas the fibers spun at high temperatures had a well-developed fibrillar texture. Anisotropy of the fibers, as evidenced by dichroism and by the variation of brightness or darkness of the fibers between crossed polars, was significantly higher for those spun at relatively high temperatures. Scanning electron microscopy revealed that the fibers spun at relatively low temperatures had poorly oriented, nonuniform morphology. Those produced at relatively high temperatures, on the other hand, consisted of well-developed fibrils. X-ray diffraction patterns showed that the molecular orientation increased with increasing extrusion temperature. A model for the development of fiber structure from thermotropic liquid-crystalline polymers is proposed.     

Preparation and liquid-crystalline properties of toluene-4-sulphonyl urethane of hydroxypropylcellulose

Abstract

A novel liquid-crystalline polymer, the toluene-4-sulphonyl urethane of hydroxypropylcellulose (TSUHPC), was prepared through chemical modification of hydroxypropylcellulose (HPC) of M_w = 60000 g mol^?1. The resulting polymer was characterized by infrared spectroscopy, differential scanning calorimetry (DSC) and polarizing microscopy. It was found that thermotropic liquid crystal phases are formed between about 60°C and 110°C. Concentrated solutions of TSUHPC in acetone and N,N-dimethylacetamide exhibit cholesteric behaviour, at room temperature. When approaching the lyotropic mesophase to solid transition, either by cooling or by solvent evaporation, very interesting arborescent structures of a seemingly fractal nature may be observed, depending on the kinetics of the transition. A banded texture can be observed when the polymer is sheared near the transition to the isotropic phase.     

THE MORPHOLOGY AND STRUCTURE OF POLYETHYLENE TEREPHTHALATE SPHERULITES

The morphology and structure of three types of normal and abnormal spherulites of polyethylene terephthalate cast from solution in dimethylphthalate were studied by polarizing microscopy, transmission electron microscopy and electron diffraction techniques. In the normal negative spherulites the [0]~* direction is parallel to the radius direction. In the normal positive spherulites the radius direction is parallel to the [6]~*. In the abnormal PET spherulites the Maltese cross extinction pattern in the polarizing microscope under crossed polars is oriented at 45°to the polars and there are concentric extinction rings around the center of the spherulite. Electron diffraction pattern indicates that [2]~* is parallel to the radius of the spherulite and this explains the observed extinction pattern, in the abnormal spherulite.     

Simultaneous optical observation of anisotropic texture for a concentrated solution of poly(γ-benzyl-l-glutamate) under transient stress response in shear flow

Simultaneous optical observation of anisotropic texture was performed under transient stress response in shear flow for a concentrated solution of poly(γ-benzyl-l-glutamate) (PBLG). Transient stress of the PBLG solution immediately after the onset of the shear flow showed a remarkable stress overshoot and damping oscillation behavior, followed by a steady state. On the other hand, simultaneous observation of the polarized optical microscopy showed the remarkable distortion of the banded texture immediately after the onset of the shear flow and the periodical changes in the retardation followed by a steady texture of the PBLG solution. The remarkable stress overshoot and the damping oscillation are closely related to the distortion of the banded texture and to the changes in the orientation of the rod-like molecules of the PBLG, respectively. Received: 15 December 1999/Accepted: 12 July 2000     

Quenched disorder in a liquid-crystal biosensor: adsorbed nanoparticles at confining walls

We analyze the response of a nematic liquid-crystal film, confined between parallel walls, to the presence of nanoscopic particles adsorbed at the walls. This is done for a variety of patterns of adsorption (random and periodic) and operational conditions of the system that can be controlled in experimental liquid-crystal-based devices. We compute simulated optical textures and the total optical output of the sensor between crossed polars, as well as the correlation function for the liquid-crystal tensor order parameter; we use these observables to discuss the gradual destruction of the original uniform orientation. For large concentrations of particles adsorbed in random patterns, the liquid crystal at the center of the sensor adopts a multidomain state, characterized by a small correlation length of the tensor order parameter, and also by a loss of optical anisotropy under observation through crossed polars. In contrast, for particles adsorbed in periodic patterns, the nematic at the center of the cell can remain in a monodomain orientation state, provided the patterns in opposite walls are synchronized.     

Optical and electrooptical properties of homeoplanar layers of cholesteric liquid crystals

Abstract

A wedge shaped layer of a cholesteric liquid crystal, with the director surface orientations first planar and the other homeotropic, shows two distinctive textures depending on the relation between the local thickness, d, and the equilibrium pitch, P ₀. If d/P ₀ < 1, the texture does not show any domains; the director distribution is reminiscent of a corkscrew. If d/P ₀ > 1, there are linear periodic domains. The domain direction rotates as the thickness of the layer increases. The voltage dependence of light transmission of the homeoplanar cholesteric layer placed between crossed polarizers is less pronounced and more linear than the corresponding dependence for the twisted nematic effect.     

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.     

Formation of band textures in hydroxypropylcellulose liquid crystals

Upon shearing, some polymeric liquid crystals develop a particular texture, called “band texture,” consisting of fine equidistant black lines as viewed between crossed polarizers. In mesomorphic hydroxypropylcellulose–water solutions, these bands are due to relaxation of the shear. The band texture appears after shearing at low shear rates and seems to exist during shearing at high shear rates (> 200 S^?1). In the latter case, the steady-state first normal-stress difference is negative. The bands relax in a few minutes and parts of the bands form elongated domains. This texture gives a H_v light-scattering pattern which can be interpreted by the theory of scattering by anisotropic rods. These domains lose their elongated shape with time.     

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     

Optical pattern simulations for closed cylinders of liquid crystals

Abstract

Optical patterns for the polarizing microscope textures of closed cylinders of liquid crystals (CCLCs) are studied by the Jones vector formulation. The simulated director configuration diagram of a CCLC with normal orientation at the walls contains four kinds of stable director configurations. The resulting texture under some approximations depends only on phase shifts. The patterns are characterized by dark brushes that coincide with the directions of the crossed polarizers. Additionally, there are concentric circle fringes. For the ring defect structure, the centre region of the cylinder exhibits a black extinction. However, this is not distinguishable as between the hyperbolic and radial structures for both the point and the ring defect patterns. Comparing the observed patterns with the simulated ones, we find that the dark cross brushes and the centre black extinction of simulated patterns are similar to those that are observed. However, the concentric circle fringes of the observed pattern are not in accordance with the simulated pattern.     

NMR study of the long time,defect-controlled,magnetic reorientation of a nematic polymer liquid crystal

Abstract

The magnetic field reorientation of an initially aligned sample of a nematic polymer liquid crystal was followed by proton NMR. Evolution to a metastable (banded) state was considered using a Rheo-NMR technique developed previously. Late stage reorientation was studied by taking into account the dynamics of defects following the formation of splay–bend walls. NMR spectra simulation allowed us to obtain the wall density as a function of time. This result, together with a defect-controlled wall dissolution model proposed by Rey [1], was used to complement the Rheo-NMR technique of measuring the viscoelastic parameters of nematic polymer liquid crystals.     

Hydrocarbon Type Separation of Lubricating Base Oil in Multigram Quantity by Preparative HPLC

Abstract

A preparative High Pressure Liquid Chromatography (HPLC) method has been developed to separate lubricating base oil into its three major hydrocarbon fractions: saturates, aromatics, and polars. The results are directly comparable to ASTM Method D2007, hydrocarbon type analysis by gradient elution liquid chromatography. The new method employs a preparative HPLC unit with dual, radially compressed columns consisting of clay and alumina/silica gel columns. Multigram quantities of minor components (1 to 2% by wt.) of a base oil can be isolated for further study.