Azimuthal anchoring energy at the interface between a nematic liquid crystal and a PTFE substrate

The azimuthal anchoring energy of the nematic liquid crystal 4-pentyl-4'-cyanobiphenil (5CB) on a poly(tetrafluoroethylene) (teflon, PTFE) film is measured for the first time. The PTFE film is deposed using the Wittmann and Smith technique which consists on rubbing a bar of this polymer against a glass substrate at a controlled temperature and pressure. Measurements of the azimuthal anchoring energy are made with a reflectometric technique which provides high accuracy and sensitivity. The dependence of the azimuthal anchoring energy on temperature and on the rubbing pressure is investigated. The extrapolation length remains virtually constant in the whole temperature range of the nematic phase except for an increase of 25% close to the clearing temperature. The azimuthal anchoring energy is somewhat strong and increases with increasing the deposition pressure of PTFE. The observation of a relevant pre-transitional anisotropy of the reflection coefficients in the isotropic phase proves that the surface interactions favor an excess of orientational order. Ageing of the anchoring energy and gliding of the easy axis are experimentally observed. Both these phenomena suggest the presence of an anisotropic adsorbed layer of nematic molecules on the PTFE film.     

Influence of the flow on the anchoring of nematic liquid crystals on Langmuir-Blodgett monolayers studied by optical second-harmonic generation

The influence of capillary flow on the alignment of the nematic liquid crystal 5CB on fatty acid Langmuir-Blodgett monolayers was studied by optical second-harmonic generation (SHG). The surface dipole sensitivity of the technique allows probing the orientation of the first liquid crystal monolayer in the presence of the liquid crystal bulk. It was found that capillary flow causes the first monolayer of liquid crystal molecules in contact with the fatty acid monolayer to be oriented in the flow direction with a large pretilt (78 degrees), resulting in a quasi-planar alignment with splay-bend deformation of the nematic director in the bulk. The large pretilt angle also suggests that the Langmuir-Blodgett film itself is affected by the flow. The quasi-planar flow-induced alignment was found to be metastable. Once the flow ceases, circular domains of homeotropic orientation nucleate in the sample and expand until the whole sample becomes homeotropic. This relaxation process from flow-induced quasi-planar to surface-induced homeotropic alignment was also monitored by SHG. It was found that in the homeotropic state the first nematic layer presents a pretilt of 38 degrees almost isotropically distributed in the plane of the cell, with a slight preference for the direction of the previous flow. Received 8 November 2000 and Received in final form 12 March 2001     

Energetics of 2D colloids in free-standing smectic-C films

The formation of regular colloid patterns in free-standing smectic films at the transition from the smectic-C to the isotropic or nematic phase is well known experimentally. The self-organization of isotropic or nematic droplets is caused by their mutual interaction, mediated by elastic distortions of the local director in the surrounding liquid crystal. These distortions are related to the anchoring conditions of the director at the droplet border. We describe analytically the energetics of the liquid crystal environment of a single droplet in one-constant approximation. A method of complex analysis, Conformal Mapping, is employed. Following a suggestion of Dolganov et al. (Phys. Rev. E. 73, 041706 (2006)), energetics of chain and grid patterns built from the colloids are investigated numerically in order to explain experimentally observed formations and their director fields.     

Temperature dependence of the effective anchoring energy for a nematic-ferroelectric interface

Specific features of the anisotropic interaction between a nematic mixture and a polar surface of a ferroelectric triglycine sulfate crystal have been studied over a wide temperature range including the substrate's Curie point T_c. The mixture was composed of two nematic liquid crystals, 60% of p-methoxybenzylidene-p-n-butylaniline (MBBA) and 40% of p-ethoxybenzylidene-p-n-butylaniline (EBBA), and doped with a small amount of a dichroic dye. The temperature dependence of the polarized components of optical density D_j of the dye absorption band for the nematic and isotropic phases of the MBBA+EBBA mixture has been obtained using polarization optic techniques. The temperature-induced structural changes in the nematic layer near T_c were found to be related to the changes in the orientational part of the tensor order parameter Q_ik. The experimental data have been interpreted using the model, in which the dispersive van der Waals forces of the substrate stabilize the planar orientation of the nematic in the bulk competing with the short-range anchoring forces in the vicinity of T_c. At the same time, the anisotropic part of the surface energy has two terms with the orthogonal easy axes. The nature of the surface electric field and its effect on the director alignment at the interface have been clarified. Taking into account the known relation between anchoring strength and the nematic order parameter, the effective anchoring energy w_eff for the studied system has been determined as a function of temperature.     

Periodic saddle-splay Freedericksz transition in nematic liquid crystals

By use of a local stability criterion recently introduced, we predict the existence of a periodic saddle-splay Freedericksz (PSSF) transition that adds to the existing class of classical Freedericksz transitions driven in a nematic cell by an external field. Occurrence of the PSSF transition requires a saddle-splay elastic constant with a large enough magnitude and different anchoring strengths at the plates confining the nematic cell. Otherwise, either the PSSF transition does not occur at all, or it requires a field higher than that associated with the classical aperiodic splay Freedericksz (ASF) transition, in which case it is not observable. Here, we determine the threshold field for which the PSSF precedes the ASF transition, as well as the structure of the destabilizing mode.     

Destabilizing effect of a surface electric field generated by ionic adsorption on the molecular orientation of nematic liquid crystals

The destabilizing effect of a surface electric field, produced by selective ionic adsorption, on the molecular orientation of a nematic-liquid-crystal sample is analyzed for a cell in the shape of a slab of thickness d. The electric-field distribution considered in the analysis is the one obtained in the limit in which essentially all the positive ions are adsorbed. Because of the coupling of this surface field with the nematic director, the surface anchoring energy depends on the thickness of the sample as well as on the adsorption energy characterizing the surfaces. A relation connecting the threshold field for the destabilization of the homeotropic pattern to the adsorption energy and to the thickness of the sample is established in closed form, after solving a set of two coupled non-linear equations determining the electric-field distribution across the sample. It is shown that the values of surface electric field generated by adsorbed ions that can lead to a destabilization of the homeotropic alignment can be attained by real samples.     

X-ray scattering study of the electric-field-induced layer deformations of an antiferroelectric Liquid Crystal

The effect of an external electric field on the local layer structure is investigated in the SmC^* _A, SmC^* _FI and SmC^* phases using X-ray diffraction. X-ray scattering and spontaneous polarization measurements are performed under several increasing (and decreasing) steps of AC applied voltage. The effects of the electric field differ significantly from one phase to the other. The chevron-to-bookshelf transition occurs abruptly at a high field value in the SmC^* _A phase whereas layer deformations are more progressive and occur at lower field values in the other phases. Comparison of the different behaviours suggests that the destruction of the chevron structure is mainly affected by the local molecular order. Received 16 July 2001 and Received in final form 7 December 2001     

The roughening transition of vicinal surfaces

Facetting of a vicinal surface is due to an arrangement of parallel primary steps which is commensurate with the substrate in plane periodicity (for instance one step every pth atomic row). It was shown by [#!Grempel!#] that such a locking requires an interaction between steps together with a finite step stiffness. But this early approach only reveals part of the story, as it is limited to sharp solid-vacuum interfaces in which thermal excitation of energetically expensive kinks controls all fluctuations. In this paper the problem is taken afresh in a language which applies equally well to “soft” interfaces, with important changes in the conclusions. Received 26 June 2001     

Adsorption of hydrophobic polyelectrolytes onto oppositely charged surfaces

We present a scaling theory for the adsorption of a weakly charged polyelectrolyte chain in a poor solvent onto an oppositely charged surface. Depending on the fraction of charged monomers and on the solvent quality for uncharged monomers, the globule in the bulk of the solution has either a spherical conformation or a necklace structure. At sufficiently high surface charge density, a chain in the globular conformation adsorbs in a flat pancake conformation due to the Coulombic attraction to the oppositely charged surface. Different adsorption regimes are predicted depending on two screening lengths (the Debye screening length monitored by the salt concentration and the Gouy-Chapman length monitored by the surface charge density), on the degree of ionization of the polymer and on the solvent strength. At low bulk ionic strength, an increase in the surface charge density may induce a transition from an adsorbed necklace structure to a uniform pancake due to the enhanced screening of the intra-chain Coulombic repulsion by the counterions localized near the surface. Received 12 April 2001     

Influence of surface ordering on the wetting of structured liquids

The substrate is shown to induce substantial ordering in diblock copolymer thin films above the bulk order-disorder transition (ODT) where, thermodynamically, a phase mixed state is favored. Initially, uniform films reorganize to form a hierarchy of transient surface patterns and stable film thicknesses that depend on the initial film thickness and on the substrate. Self-consistent field calculations of the free energy of the system for different situations, depending on the relative tendency for the different block components to be attracted to the substrate and/or free surface, provide an explanation of the formation of the stable film thicknesses. A continuum picture proposed earlier by Brochard et al.rovides an explanation of the wetting characteristics of this system. In some cases the ordering destabilizes the film so that dewetting occurs (wetting autophobicity), whereas in other cases the surface ordering results in a kinetic stabilization of a film that would otherwise dewet. Received 3 August 2001 and Received in final form 1 November 2001     

Temperature effects on capillary instabilities in a thin nematic liquid crystalline fiber embedded in a viscous matrix

Linear stability analysis of capillary instabilities in a thin nematic liquid crystalline cylindrical fiber embedded in an immiscible viscous matrix is performed by formulating and solving the governing nemato-capillary equations, that include the effect of temperature on the nematic ordering as well as the effect of the nematic orientation. A representative axial nematic orientation texture with the planar easy axis at the fiber surface is studied. The surface disturbance is expressed in normal modes, which include the azimuthal wave number m to take into account non-axisymmetric modes. Capillary instabilities in nematic fibers reflect the anisotropic nature of liquid crystals, such as the ordering and orientation contributions to the surface elasticity and surface normal and bending stresses. Surface gradients of normal and bending stresses provide additional anisotropic contributions to the capillary pressure that may renormalize the classical displacement and curvature forces that exist in any fluid fiber. The exact nature (stabilizing and destabilizing) and magnitude of the renormalization of the displacement and curvature forces depend on the nematic ordering and orientation, i.e. the anisotropic contribution to the surface energy, and accordingly capillary instabilities may be axisymmetric or non-axisymmetric. In addition, when the interface curvature effects are accounted for as contributions of the work of interfacial bending and torsion to the total energy of the system, the higher-order bending moment contribution to the surface stress tensor is critical in stabilizing the fiber instabilities. For the planar easy axis, the nematic ordering contribution to the surface energy, which renormalizes the effect of the fiber shape, plays a crucial role to determine the instability mechanisms. Moreover, the unstable modes, which are most likely observed, can be driven by the dependence of surface energy on the surface area. Low-ordering fibers display the classical axisymmetric mode, since the surface energy decreases by decreasing the surface area. Decreasing temperature gives rise to the encounter with a local maximum or to monotonic increase of the characteristic length of the axisymmetric mode. Meanwhile, in the presence of high surface ordering, non-axisymmetric finite wavelength instabilities emerge, with higher modes growing faster since the surface energy decreases by increasing the surface area. As temperature decreases, the pitches of the chiral microstructures become smaller. However, this non-axisymmetric instability mechanism can be regulated by taking account of the surface bending moment, which contains higher order variations in the interface curvatures. More and more non-axisymmetric modes emerge as temperature decreases, but, at constant temperature, only a finite number of non-axisymmetric modes are unstable and a single fastest growing mode emerges with lower and higher unstable modes growing slower. For nematic fibers, the classical fiber-to-droplet transformation is one of several possible instability pathways, while others include chiral microstructures. The capillary instabilities' growth rate of a thin nematic fiber in a viscous matrix is suppressed by increasing either the fiber or matrix viscosity, but the estimated droplet sizes after fiber breakup in axisymmetric instabilities decrease with increasing the matrix viscosity. Received 15 April 2002 and Received in final form 3 October 2002 RID="a" ID="a"e-mail: alejandro.rey@mcgill.ca     

Colloidal inclusions in smectic films with spontaneous bend

Inclusions in free-standing smectic films are simple model systems for two-dimensional anisotropic dispersions. From theory and experiment, different topologies of elastic distortions of the embedding liquid crystal are known. Quadrupolar and different dipolar defect configurations in the vicinity of the inclusion are possible, and these configurations determine the type of interactions between the inclusions. The quadrupolar configuration is often energetically preferred. We show, however, that dipolar director configurations around inclusions can be energetically favourable over quadrupolar arrangements in chiral smectics, as a consequence of a spontaneous-bend term in the elastic-energy formulation. As the inclusion size influences the selection of the deformation types, the corresponding spontaneous-bend constant can be estimated for the strong anchoring limit if the c -director fields around inclusions of different diameters are taken into account.     

Colloids on free-standing smectic films

We study the structure of a free-standing smectic-A film around a micron-size polystyrene colloid adsorbed onto the film. We find that a colloid or a cluster of colloids is surrounded by an optically distinct and radially decorated meniscus ending with a sharp edge. The observed strong and finite-range attraction between the adsorbed colloids is driven by the fusion of menisci. We interpret the structure of the smectic meniscus in terms of a model dominated by the surface free energy and we argue that the characteristic appearance of the meniscus is due to layer undulations.     

Faceting and stability of smectic A droplets on a solid substrate

It is shown that a smectic A droplet deposited on a solid substrate treated for strong homeotropic anchoring is faceted at the top in spite of the fact that there are no steps at the free surface, but instead edge dislocations in the bulk. The radius of the facet and the full profile of the curved part of the droplet are determined as a function of the temperature in the vicinity of a nematic-smectic A phase transition. It is shown that the observed profiles do not correspond to the actual equilibrium shape, but to metastable configurations close to their point of marginal stability. In addition, we predict that the profiles must be different for a given temperature depending on whether the droplet has been heated or cooled down to reach this temperature. Finally, we discuss the problem of the formation of giant dislocations in big droplets (Grandjean terraces).     

Discotic molecules in cylindrical nanopores: A Monte Carlo study

We report Monte Carlo simulations of a model discotic molecule embedded in cylindrical pores. We consider a planar anchoring of the molecules on the surface for two different cylinder radii: R ^* = 5 and R ^* = 10 , in units of the molecular diameter. For both radii, we note that the system is progressively structured in concentric shells when decreasing the temperature. With the small radius, we observe continuous transitions from an isotropic to a nematic phase and then to a crystal one. The radius of the pores is sufficiently small to force the crystal to grow along their main axis. However some orientational discrepancies are observed: some samples present a zigzag configuration. With the big radius, the situation is more complex and it is likely that different scenarios are available. The crystals can be built along the main axis of the cylinders, as for the small radius, but also in any other direction. Thus we observe samples with different orientational domains. In the case of crystals oriented along the nanopore axis, we note that only the first 5 shells close to the wall are sensitive to it.     

Structure and polarity of 8CB films evaporated onto solid substrates

Brewster-angle reflection ellipsometry and surface optical second harmonic generation were used to study the growth of 4'-n-octyl-4-cyanobiphenyl (8CB) films evaporated in air onto polymeric and quartz glass substrates. The layer-by-layer growth of the films terminates after formation of two distinctive interfacial layers. Both of these two layers are polar and tilted. In the first layer the molecules lie nearly flat on the surface, while in the second layer they point on average about 50° toward the surface normal. The dipole moment of the second layer has a lower magnitude and an opposite direction with respect to the dipole moment of the first layer.     

Distortion and unwinding of the helical structure in polymer-stabilized short-pitch ferroelectric liquid crystal

We report the effect of an anisotropic polymer network formed from an achiral photoreactive monomer in a short-pitch chiral SmC* phase on the distortion and the unwinding of the helical structure of the ferroelectric phase. The electro-optical behaviour and ferroelectric properties were experimentally determined for films containing various polymer concentrations. The critical field, E_u, for the transition from the distorted structure to the homogeneous state was measured as a function of polymer concentration. A linear increase of E_u versus polymer concentration was observed, showing that the helical structure of the short-pitch SmC* phase was stabilized by the polymer network. This behaviour was expected to be a consequence of the increase of the apparent elastic constants of the ferroelectric liquid crystal stabilized by the anisotropic polymer network films. The polymer network morphology was investigated using atomic-force microscopy, revealing a twisted structure of the polymer fibers. This twisted structure was transferred onto a polymer network during the polymerization process within a short-pitch SmC* phase. The increase of the apparent elasticity can then be interpreted by a strong interaction between polymer network and the liquid-crystal molecules. From our experimental data, the coupling coefficient, W_p, characterizing this interaction was evaluated for all studied polymer concentrations.     

Poling of liquid crystals in thin films

We examine the effect of a strong DC electric field on the molecular orientational order and the nonlinear optical response of liquid crystals in thin films. We compare the results of second-harmonic generation measurements with the predictions of two models, one assuming that the dipoles carried by the molecules have no interactions (the isotropic model), and the other assuming that the dipoles evolve in a Maier-Saupe orienting field responsible for the liquid-crystalline order (the Maier-Saupe model). In both cases, we take into account the effect of surfaces and confinement on the behavior of the molecules. We find that the molecular dipoles behave as predicted by the isotropic model, but that their reorientation is correlated in such a way that the apparent dipole moment of the reorienting units is one order of magnitude larger than the molecular dipole moment. Received: 13 December 2002 / Accepted: 22 April 2003 / Published online: 21 May 2003 RID="a" ID="a"Also at FOM-Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands. RID="a" ID="a"Also at FOM-Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands. RID="b" ID="b"e-mail: jerome@science.uva.nl     

Structure and frustration in liquid crystalline polyacrylates I. Bulk behaviour

The phase behaviour and structure are reported of a new type of frustrated side-chain liquid crystalline (LC) polymer, a polyacrylate with phenylbenzoate mesogenic side groups and a narrow polydispersity. At a high degree of polymerisation the LC polymers show a nematic, a smectic-A_d, a re-entrant nematic and a C phase, for shorter chains only a nematic and a C phase. This constitutes a new example of nematic re-entrance for which the driving field is the length of the polymer chain. The smectic-A_d layers consist of partially overlapped side groups while in the C phase the side chains are rearranged into chevron-like blocks of bilayers. We propose an explanation of the frustrated phase behaviour in terms of these two different competing length scales and their coupling to the backbone conformations. Received 28 February 2001 and Received in final form 6 August 2001