Stability of thin nematic films

We discuss the peculiarity of thin nematic films on solid substrates with a free surface, underlining the differences with what is usually seen in dewetting. We review the thermodynamic basis of the coupled phase/thickness separation that has previously been shown experimentally. We give new experimental evidences for the origin of the coupling force chosen in our previous theoretical model. This additional information contributes to the discussion raised by the article of Ziherl and Zumer in this issue [19].Received: 3 December 2003PACS: 68.15. + e Liquid thin films - 64.70.Md Transitions in liquid crystals - 61.30 Surface phenomena in liquid crystals including anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions and wetting transitions     

Stripe instability in thin films of smectic liquid-crystal polymers

Two-dimensional nanostripes are formed in thin films of side-chain liquid-crystalline polymer films when the material enters the smectic phase. The structure is investigated using transmission electron microscopy. Electron diffraction patterns show that the chain molecules are mostly aligned in the film plane and the average molecular director is parallel to the direction of the stripes. We discuss factors affecting the stripe amplitude and periodicity, such as the film thickness and the temperature of annealing in the nematic phase, and suggest a possible mechanism for their formation. We propose that an equilibrium instability occurs due to a competition between the layer-aligning effect of the substrate and the planar director alignment, forcing smectic layers perpendicular to the film surface. The stripes decorate the overall patterns of nematic director in the polymer film and provide a means of high-resolution imaging for observation of textures and disclinations.Received: 10 June 2003, Published online: 19 August 2003PACS: 68.37.Lp Transmission electron microscopy (TEM) (including STEM, HRTEM, etc.) - 61.30.Vx Polymer liquid crystals - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 68.55.Nq Composition and phase identification     

Random anisotropy nematic model: Connection with experimental systems

We study theoretically the phase behavior of the continuum Random Anisotropy Nematic model. A domain-type pattern is assumed to appear in a distorted nematic liquid crystal (LC) phase. We map the model parameters to physical quantities characterizing LCs confined to Controlled-Pore Glasses and LC-aerosil dispersions. The domain size dependence on the disorder strength is obtained in accordance with the Imry-Ma prediction. The model estimates for temperature shifts of the paranematic-nematic phase transition and for the critical point, where this transition ceases to exist, are compared to the available experimental results.Received: 28 March 2004, Published online: 29 June 2004PACS: 61.30.-v Liquid crystals - 61.30.Dk Continuum models and theories of liquid crystal structure - 61.30.Gd Orientational order of liquid crystals; electric and magnetic field effects on order - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions     

Dewetting of polymeric films: unresolved issues

Since the early seminal theoretical work by Brochard and coworkers, and experiments by Reiter over a decade ago, considerable progress has been made toward the development of a comprehensive picture of the equilibrium and dynamic behavior of unstable thin polymeric films. Generally, theoretical work has carefully guided the design of many experiments conducted in this field. Recent experimental findings, however, raise new questions that could probably not have been foreseen by theory and now need to be revisited. In this paper we highlight three problems in two general areas, (1) the use of the effective interfacial potential describing film substrate interactions and (2) the dynamics of dewetting and the associated connection to slip phenomena and fingering instabilities. We suggest that in addition to experiments, analytical theory and simulations will play a critical role toward elucidating the ultimate goal of a universal picture of equilibrium and dynamic behavior of instabilities in thin films.Received: 1 August 2003PACS: 68.15. + e Liquid thin films - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions     

Dynamical behaviour of holographic gratings with a nematic film --Polymer slice sequence structure

We have studied the dynamical response of a new kind of holographic grating to a pulsed electric field. The structure, named POLICRYPS, consists of a sequence of homogeneous polymer slices separated by liquid-crystal films. We have found that both the rise and fall response times depend on the pulse duration and amplitude of the applied electric field. We propose a phenomenological explanation for this behaviour, outlining the possibility of getting response times of the order of 100 s by properly choosing the pulse shape. Results are very interesting for developments in which POLICRYPS gratings could be proposed as basic elements in photonic devices for telecom applications, and induce to a deeper analysis of the microscopic interaction between liquid crystal and polymer interfaces in these samples.Received: 5 February 2004, Published online: 14 September 2004PACS: 61.30.Pq Microconfined liquid crystals: droplets, cylinders, randomly confined liquid crystals, polymer dispersed liquid crystals, and porous systems - 42.40.Eq Holographic optical elements; holographic gratings - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions     

Static and dynamic electro-optic properties of a SmC* phase in surface stabilized geometry and dispersed in the polymer matrix

Comparative electro-optical measurements have been made on a ferroelectric liquid crystal (FLC) in surface stabilized geometry and confined to an ellipsoidal cavity within a polymer matrix. The static and dynamic electro-optical characteristics were measured for both systems and show qualitatively similar behaviours. A fast switching and important bistability were observed and characterized as a function of the applied electric field strength. The switching time between the two stable states of the surface stabilized cell was found to be longer than that found for the composite films. We argue that the faster switching dynamic of the FLC in cavities is due to the enhance of the rotational mobility of the molecules, probably (and partly) because of the soft anchoring character of the molecules at the cavity walls. Using a collective switching model in the high field regime, which assume a linear coupling between the spontaneous polarization and the local cavity electric field, we give an estimate of the rotational viscosity of the FLC molecules in the droplets.Received: 5 October 2003, Published online: 5 February 2004PACS: 61.30.Pq Microconfined liquid crystals: droplets, cylinders, randomly confined liquid crystals, polymer dispersed liquid crystals, and porous systems - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 77.80.Fm Switching phenomena     

Frustrated rotations in nematic monolayers

Tabe and Yokoyama found recently that the optical axis in a chiral monolayer of a ferronematic rotates when water evaporates from the bath: the chiral molecules act as propellers. When the axis is blocked at the lateral walls of the trough, the accumulated rotation inside creates huge splays and bends. We discuss the relaxation of these tensions, assuming that a single dust particle nucleates disclination pairs. For the simplest geometry, we then predict a long delay time followed by a non-periodic sequence of bursts. These ideas are checked by numerical simulations.PACS: 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 61.30.Jf Defects in liquid crystals     

Thickening of a smectic membrane in an evanescent X-ray beam

We report an unusual thickening of smectic membranes under the influence of X-ray irradiation below the critical angle. In the case of a four-layer film the thickness was found to grow at the footprint of the beam, reaching within minutes tens of layers. The effect is attributed to the localized energy dissipation of the evanescent wave. The island thus created is not connected to the meniscus and after the beam is switched off the film returns to its original state. A possible explanation is given in terms of a local disrupture of the tension of the smectic membrane.Received: 22 July 2004, Published online: 1 October 2004PACS: 61.30.-v Liquid crystals - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 52.25.Os Emission, absorption, and scattering of electromagnetic radiation     

Isotropic-nematic interface and wetting in suspensions of colloidal platelets

We study interfacial phenomena in a colloidal dispersion of sterically stabilized gibbsite platelets, exhibiting coexisting isotropic and nematic phases separated by a sharp horizontal interface. The nematic phase wets a vertical glass wall and polarized light micrographs reveal homeotropic surface anchoring both at the free isotropic-nematic interface and at the wall. On the basis of complete wetting of the wall by the nematic phase, as found in our density functional calculations and computer simulations, we analyze the balance between Frank elasticity and surface anchoring near the contact line. Because of weak surface anchoring, the director field in the capillary rise region is uniform. From the measured rise (6 microm) of the meniscus at the wall we determine the isotropic-nematic surface tension to be 3 nN/m, in quantitative agreement with our theoretical and simulation results.     

Surface and bulk interchange energy in binary mixtures of chain molecules

The interchange (interaction) parameter, controlling the phase behaviour of a binary mixture, is determined for the bulk and the surface of binary mixtures of different types of chain molecules, using surface tensiometry and a mean-field theory. For all mixtures and concentrations studied an identical behaviour is observed at the surface, depending only on the square of the reduced chain length mismatch , where and are the difference in and average of the number of carbons of the two components.Received: 21 December 2003, Published online: 25 March 2004PACS: 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 68.35.Md Surface thermodynamics, surface energies - 68.03.Cd Surface tension and related phenomena     

Changes of thermo-morphologic and thermotropic properties of liquid crystals at direct and reverse nematic mesophase ↔ isotropic liquid phase transitions: surface-induced effect

In this work, the effect of thin films on the thermo-morphologic and thermotropic properties of the phase transitions between the nematic mesophase and isotropic liquid has been investigated. Investigations have been carried out for both the heating and cooling processes. The temperature and linear widths of the biphasic regions of the direct and reverse phase transitions in nematic liquid crystals versus thickness of the thin films have been calculated with a high accuracy. The shift of the nematic mesophase–isotropic liquid and the isotropic liquid–nematic mesophase phase transition temperatures to higher temperatures and the enlargement of the temperature and linear widths of the biphasic regions as the effect of surfaces have been found.     

Enhancement of the orientational order parameter of nematic liquid crystals in thin cells

We report measurements of birefringence of several nematic liquid crystals having transverse as well as longitudinal dipole moments in thin (1.4 to ) and thick (7 to cells. Rubbed polyimide-coated glass plates are used to get planar alignment of the nematic director in these cells. We find significant enhancement (6 to ) of ( , where S is the orientational order parameter) in thin cells in all compounds with aromatic cores even at temperatures far ( C) below the nematic-isotropic transition point. The enhancement is larger in compounds having several phenyl rings and lower if the number of phenyl rings is reduced. In a compound that does not have an aromatic core no significant enhancement is observed, implying that the strength of the surface potential depends on the aromaticity of the cores. Assuming a perfect orientational order at the surface, calculations based on the Landau-de Gennes theory show that the thickness averaged enhancement of S is sharply reduced as the temperature is lowered in the nematic phase. The measured order parameter S is further enhanced in thin cells because of the stiffening of the elastic constant which reduces the thermal fluctuations of the nematic director. The combined effect is however too small at low temperatures to account for the experimental data.Received: 22 February 2004, Published online: 24 May 2004PACS: 61.30.-v Liquid crystals - 61.30.Pq Microconfined liquid crystals: droplets, cylinders, randomly confined liquid crystals, polymer dispersed liquid crystals, and porous systems - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitionsSurajit Dhara: Present address: Department of Physics, Birla Institute of Technology and Science, Pilani 333 031, India.     

Anchoring transitions with polar and non-polar nematic liquid crystals on incompletely oxidized silane substrates

The active oxygen gas arising from a plasma reactor is used to realize progressive chemical modifications onto silane coatings that could be particularly interesting as alignment layers for liquid crystal display applications. Depending on the oxygen density grafted onto the substrate, these alignment layers provide different zenithal anchoring angles, or pretilt angles, with anchoring transitions, for polar and non-polar nematic liquid crystals as 5CB and MBBA, respectively. The anchoring transitions are found to be smoother with the polar nematics. Such a behavior is discussed in terms of the differential wetting model by adding a cosine term to the interaction energy between the nematic and the substrate. A local justification is proposed for this symmetry breaking term. Received: 18 May 1998     

The structural transitions in ferronematics and ferronematic droplets

The paper presents an overview of the observations of structural transitions in ferronematic based on thermotropic nematic 6CHBT (4-trans-4′-n-hexyl-cyclohexyl-isothiocyanato-benzene) and in ferronematic droplets. The type of anchoring was determined using the results of the capacitance measurements. The ferronematic droplets were observed in solutions of nematogenic 6CHBT with fine magnetic particles and phenyl isocyanate. The phase diagram of the transitions between isotropic and nematic phases was found. The magneto-dielectric measurements of various structural transitions in this new system enabled to estimate the type of anchoring of nematic molecules on magnetic particles surfaces in droplets.     

Anchoring transitions of nematic liquid crystals

A crystalline substrate such as mica or gypsum can orient a thin layer of nematic liquid crystal spread on top. By adsorbing one or more other kinds of molecules onto the surface, we have observed transitions in the orientation of the molecules on the surface. These “anchoring transitions” are analyzed via Landau-Ginzburg theory and may be first or second-order. The second-order anchoring transition is the first two-dimensional system where critical fluctuations may be observed optically.     

Blobs,channels and “cigars”: Morphologies of liquids at a step

We have studied the equilibria of liquid droplets wetting a step edge with an opening angle by a combination of analytical and numerical methods. Depending on the wetting properties of the substrate walls and on the liquid volume, different locally or globally stable liquid morphologies are found. Complete spreading of the liquid along the bottom edge of the step is observed at equilibrium contact angles satisfying . If the contact angle exceeds a threshold value the liquid exists in a blob-like configuration. Surprisingly, we find an intermediate regime at a sufficiently high liquid volume and in a range of contact angles , in which cigar-shaped configurations arise in addition to the blob. We close the paper by a detailed discussion of the stability of this novel liquid morphology.PACS: 47.55.Dz Drops and bubbles - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 68.08.Bc Wetting     

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.     

Liquid crystal films on curved surfaces: An entropic sampling study

The confining effect of a spherical substrate inducing anchoring (normal to the surface) on rod-like liquid crystal molecules contained in a thin film spread over it has been investigated with regard to possible changes in the nature of the isotropic-to-nematic phase transition as the sample is cooled. The focus of these Monte Carlo simulations is to study the competing effects of the homeotropic anchoring due to the surface inducing orientational ordering in the radial direction and the inherent uniaxial order promoted by the intermolecular interactions. By adopting an entropic sampling procedure, we could investigate this transition with a high temperature precision, and we studied the effect of the surface anchoring strength on the phase diagram for a specifically chosen geometry. We find that there is a threshold anchoring strength of the surface below which uniaxial nematic phase results, and above which the isotropic fluid cools to a radially ordered nematic phase, besides of course expected changes in the phase transition temperature with the anchoring strength. In the vicinity of the threshold anchoring strength we observe a bistable region between these two structures, clearly brought out by the characteristics of the corresponding microstates constituting the entropic ensemble.     

Quartic coupling and its effect on wetting behaviors in nematic liquid crystals

Based on the fact that rubbed groove patterns also affect the anchoring of liquid crystals at substrates,a quartic coupling is included in constructing the surface energy for a liquid crystal cell.The phase diagram and the wetting behaviors of the liquid crystal cell,bounded by surfactant-laden interfaces in a magnetic field perpendicular to the substrate are discussed by taking the quartic coupling into account.The nematic order increases at the surface while it decreases in the bulk as a result of the introduction of quartic substrate-liquid crystal coupling,indicating that the groove anchoring makes the liquid crystal molecules align more orderly near the substrate than away from it.This causes a different wetting behavior:complete wetting.     

Surface transitions in nematic liquid crystals oriented with Langmuir-Blodgett films

In this paper two types of surface transitions in nematic liquid crystals are theoretically analyzed with a simple model in which the anchoring energy is the result of both steric and electric interactions. The physical model is proper to explain both the transition temperature experimentally observed in homeotropically aligned nematic liquid crystals, and the change in the mean molecular direction due to the variation of the number of surfactant films, piled on the boundary surfaces with the Langmuir-Blodgett technique.Partially supported by the TEMPUS program