Theory of surface excess Miesowicz viscosities of planar nematic liquid crystal-isotropic fluid interfaces

An expression for the surface excess stress tensor for planar compressible interfaces between rod-like nematic liquid crystals and isotropic viscous fluids is derived using the classical surface excess theory formalism, adapted to capture the intrinsic anisotropy of the nematic orientational ordering. A required step in the theory is to find the actual stress tensor in the three-dimensional interfacial region, which is obtained by a decomposition of the kinematic fields (rate of deformation tensor and director Jaumann derivative) into tangential, normal, and mixed components with respect to the interface. The viscosity coefficients appearing in the surface excess stress tensor are expressed in terms of interfacial and bulk viscosities for planar, constant orientation, flows. The expressions are used to define the three fundamental surface excess Miesowicz shear viscosities, in analogy with the three bulk Miesowicz shear viscosities. The ordering in the magnitudes of the surface excess Miesowicz shear viscosities is shown to depend on the magnitude of the surface scalar nematic order parameter relative to that of the adjoining bulk nematic phase. When the surface scalar order parameter is greater than in the bulk, the classical ordering in terms of magnitudes of the three bulk Miesowicz shear viscosities is recovered. On the other hand, when the surface scalar order parameter is smaller than in the bulk, the classical ordering in terms of magnitudes of the three viscosities does not hold, and inequality transitions are predicted as the surface scalar order parameter increases towards the bulk value. Received 5 July 1999 and Received in final form 16 November 1999     

Temperature-induced orientational transition of nematics on the surface of a ferroelectric crystal

A temperature-induced orientational transition is investigated in a mixture of nematic liquid crystals on the surface of a cleavage of a ferroelectric triglycine sulfate crystal. The transition has been observed by the variation of the polarized absorbance components of a dye introduced into the nematic matrix with increasing temperature. The reorientation of molecules in the liquid crystal volume confined by solid walls is due to competition between dispersion and polar forces at the surface and the decrease in the electric field of the substrate up to its complete disappearance at the ferroelectric Curie point.     

Continuous paranematic-to-nematic ordering transitions of liquid crystals in tubular silica nanochannels

The optical birefringence of rodlike nematogens (7CB, 8CB), imbibed in parallel silica channels with 10 nm diameter and 300 microm length, is measured and compared to the thermotropic bulk behavior. The orientational order of the confined liquid crystals, quantified by the uniaxial nematic ordering parameter, evolves continuously between paranematic and nematic states, in contrast to the discontinuous isotropic-to-nematic bulk phase transitions. A Landau-de Gennes model reveals that the strength of the orientational ordering fields, imposed by the silica walls, is beyond a critical threshold, that separates discontinuous from continuous paranematic-to-nematic behavior. Quenched disorder effects, attributable to wall irregularities, leave the transition temperatures affected only marginally, despite the strong ordering fields in the channels.     

Phase equilibria of confined liquid crystals

The differences between the phase diagram of the Gay-Berne potential confined by two identical walls versus the corresponding bulk phase diagram have been investigated. A wall-fluid interaction 9-3 Lennard-Jones potential was used. The study was performed in most cases by using the hybrid Monte Carlo method for the μVT ensemble. Several isotherms were analysed where vapour, liquid and smectic phases were observed. The smectic-isotropic coexistence region becomes wider, i.e. the isotropic coexistence line is shifted to lower densities but the smectic coexistence line remains nearly the same. The triple point temperature of the confined system is estimated to be in the vicinity of 0.45 versus 0.40 of the bulk system. For the isotherm at T? = 0.65 an orientational dependence was added to the 9-3 Lennard-Jones potential to model the wall-fluid interaction. For both kinds of walls, 9-3 LJ with and without orientational dependence, confinement was not found to stabilize a nematic phase as found by previous authors.     

Experimental evidence of the Halperin-Lubensky-Ma effect in liquid crystals

The orientational order parameter decrease, due to nematic director macroscopic fluctuations, is obtained by birefringence measurements around the nematic <--> smectic-A transition temperature of the liquid crystal 4'-n-octyl-4-cyanobiphenyl. The measured nematic order reduction shows the same amplitude as the secondary order parameter discontinuity at the transition providing direct evidence of the Halperin-Lubensky-Ma effect. The importance of nematic director thermal fluctuations on the character of the transition is revealed as their quenching by an electric field of approximately 20 V/micrometer restores the second order character of the transition.     

Surface effects on liquid crystals constrained in nanoscaled pores investigated by field cycling NMR relaxometry and Monte Carlo simulations

Proton relaxation rates of nematic liquid crystals confined in nanoporous cavities were measured in a broad frequency range with the help of field cycling nuclear magnetic resonance relaxometry. The shape of relaxation dispersion curves in confined materials strongly deviates from the behavior in bulk, both above and below the bulk isotropization temperature. A strong increase in relaxation rates, exceeding by two orders of magnitude that of the bulk sample, is observed in the range of a few kilohertz. Relaxation rates in bigger pores decreased. Experimental findings are interpreted in terms of surface-induced orientational order and diffusion between sites with different orientations of local directors. With the aid of Monte Carlo simulations, two processes affecting low-frequency relaxation could be identified: (a) exchange losses of molecules from the surface-ordered phase to the bulk-like phase, and (b) Reorientations Mediated by Translational Displacements, which dominate the long-time scale and account for the recovery of correlation in molecular orientations as molecules probe different surface sites. It is shown that the width of the oriented layer may strongly affect the slope of dispersion curves and that cross-over between plateau and power law dispersion regimes shifts towards lower frequencies for bigger pores.     

Fluctuations of orientational order in a uniaxial nematic liquid crystal with biaxial molecules and its response to an external field

Homogeneous thermal fluctuations of the orientational order parameters S and G of biaxial molecules in a uniaxial nematic liquid crystal are investigated in the framework of the molecular-statistical theory. It is demonstrated that the molecular biaxiality significantly affects the order parameters S and G, their temperature dependences in the nematic phase, the amplitude and the temperature dependence of the order parameter fluctuations in the nematic and isotropic phases, and the character of the transition from the nematic phase to the isotropic liquid phase. It is established that the fluctuations of the parameters S and G in the nematic phase are related to the temperature dependences of S and G and the susceptibilities χ_S and χ_G of the nematic liquid crystal to external fields, which leads to a change in the parameters S and G at a fixed director orientation. Explanations are offered for the known experimental data on the orientational ordering of biaxial molecules under the action of external fields in the isotropic phase of nematic liquid crystals.     

Two-particle microrheology of quasi-2D viscous systems

We study the spatially correlated motions of colloidal particles in a quasi-2D system (human serum albumin protein molecules at an air-water interface) for different surface viscosities eta s. We observe a transition in the behavior of the correlated motion, from 2D interface dominated at high eta s to bulk fluid dependent at low eta s. The correlated motions can be scaled onto a master curve which captures the features of this transition. This master curve also characterizes the spatial dependence of the flow field of a viscous interface in response to a force. The scale factors used for the master curve allow for the calculation of the surface viscosity eta s that can be compared to one-particle measurements.     

Quasi-long-range order in nematics confined in random porous media

We study the effect of random porous matrices on the ordering in nematic liquid crystals. The randomness destroys orientational long-range order and drives the liquid crystal into a glass state. We predict two glass phases, one of which possesses quasi-long-range order. In this state the correlation length is infinite and the correlation function of the order parameter obeys a power dependence on the distance. The small-angle light-scattering amplitude diverges but slower than in the bulk nematic. In the uniaxially strained porous matrices two new phases emerge. One type of strain induces an anisotropic quasi-long-range-ordered state while the other stabilizes nematic long-range order.     

Orientational dynamics in nematic liquid crystals

We examine the behaviour of single-particle orientational time correlation functions in nematic liquid crystals. As well as the expected dynamics involving oscillation in a mean-field potential, and occasional jumps between orientations parallel and antiparallel to the director, we provide the first simulation evidence of long-time tails characteristic of coupling to director fluctuations.     

Surface-induced order and diffusion in 5CB liquid crystal confined to porous glass.

Liquid crystals confined into small cavities are known to have a weak orientational order even above the nematic-isotropic transition temperature. The surface-induced order and molecular dynamics in this temperature range are studied with the aid of deuteron NMR spectra, spin relaxation times T(1) and T(2,) proton dipolar-correlation effect, and direct measurements of the effective diffusion coefficient for the liquid crystal 5CB confined to controlled-pore glasses. Our results show that an arrangement of molecules parallel to the wall is induced by local molecular interactions between the liquid crystal and solid, resulting in a weak and temperature independent surface order parameter, S(0) approximately 0.02 +/- 0.01. There is no indication of a significant slowing-down of molecular diffusion at the wall, neither rotational nor translational. In cavities of nanometer size, where the nematic order evolves gradually upon cooling, a broadening of the NMR linewidths due to dynamic effects should be taken into account.     

Dynamic light scattering study of biaxial ordering in a thermotropic liquid crystal

Dynamic light scattering from orientational order fluctuations in a liquid crystalline tetrapode reveals successive, weakly first-order isotropic to uniaxial and uniaxial to biaxial nematic phase transitions. The order parameter relaxation rates exhibit temperature dependences consistent with Landau-de Gennes mean field theory. Combined with previous evidence of a second-order uniaxial-biaxial transition in a closely related tetrapode, the present study supports the existence of a nematic-nematic tricritical point in thermotropic liquid crystals.     

Effect of external field on coherent backscattering in nematics

For a one-elastic-constant model of nematic liquid crystal the optical theorem is shown to produce an explicit relationship between the scattering length of extraordinary wave mode and magnetic coherence length. The Monte Carlo simulation of coherent backscattering is performed accounting for the long-range orientational fluctuations and scattering length anisotropy; the coherent backscattering peak is shown to change quite weakly while the magnetic field varies several orders.     

Anisotropic microstructure-induced reduction of the Rayleigh instability for liquid crystalline polymers

We analyze a macroscopic 3D model for flows of liquid crystalline polymers (LCPs), deduced from Doi-type [3,4] kinetic equations. The Doi model accounts for rigid-rod microstructure, which introduces elastic relaxation and polymer-induced viscosity in addition to a Newtonian solvent viscosity, thus capturing all effects contained in standard isotropic viscoelastic models for Maxwell and Oldroyd B fluids. The rod-like microstructure further introduces anisotropic effects in the form of drag on the rods, together with a short-range, Maier-Saupe intermolecular potential, whose critical points vary with LCP concentration and yield stable isotropic (at low density) and nematic (at high density) equilibrium phases. From this single model, we compare various physical mechanisms for reducing the capillary instability of inviscid cylindrical jets: solvent viscosity as studied by Rayleigh and Chandrasekhar; isotropic viscoelasticity, both with and without Newtonian solvent viscosity; anisotropic polymer friction; and finally, the nematic, highly aligned prolate phase at high LCP density. Realistic parameter values for LCPs correspond to a regime in which the LCP capillary number (polymer bulk free energy relative to surface tension) is above an identified critical value; in such regimes, the unstable growth rates of the isotropic and nematic phases are lowered arbitrarily close to zero if the molecular drag is sufficiently anisotropic even in the absence of solvent viscosity. In low capillary number regimes, where surface tension dominates LCP bulk free energy, the LCP growth rates are sandwiched below the inviscid Rayleigh curve and above an explicit positive lower bound.     

Orientational coupling amplification in ferroelectric nematic colloids

We investigated the physical properties of low concentration ferroelectric nematic colloids, using calorimetry, optical methods, infrared spectroscopy, and capacitance studies. The resulting homogeneous colloids possess a significantly amplified nematic orientational coupling. We find that the nematic orientation coupling increases by approximately 10% for particle concentrations of 0.2%. A manifestation of the increased orientational order is that the clearing temperature of a nematic colloid increases by up to 40 degrees C compared to the pure liquid crystal host. A theoretical model is proposed in which the ferroelectric particles induce local dipoles whose effective interaction is proportional to the square of the orientational order parameter.     

Effect of local molecular ordering on the temperature behavior of the relaxation time of order-parameter fluctuations in the isotropic phase of PAA nematic liquid crystal

The behavior of the relaxation time of order-parameter fluctuations in the isotropic phase of PAA nematic liquid crystal was investigated on the basis of the spectra of depolarized (inelastic) light scattering in a wide temperature range including the immediate vicinity to the temperature of the nematic phase transition. The experimental data were analyzed within the Landau—de Gennes theory. The temperature limits of applicability of the Landau—de Gennes theory to the isotropic-phase dynamic properties are obtained. The minimum correlation length is determined, at which the effect of local ordering on the dynamics of slow orientational motion of isotropic-phase molecules is dominant.     

Orientational optical torque in a nematic liquid crystal,caused by trans- and cis-isomers of low- and high-molecular compounds

The effect of light on the conformational composition of low- and high-molecular (fifth-generation dendrimer) azobenzene dyes in a nematic host is studied. The orientational optical response of the nematic liquid crystal (NLC), caused by the presence of these compounds in the nematic host, is measured. The contributions of isomers to the orientational optical torque affecting the NLC director are determined. The results obtained suggest that the increase in the optical orientation efficiency in NLCs when using high-molecular dopants instead of low-molecular ones is unrelated to the difference in their conformational composition in the light field, but is caused by deceleration of orientational motion of chromophores.     

Fluctuational spatial dispersion in achiral liquid crystals

An investigation is made of the spatial dispersion of the permittivity of achiral liquid crystals with large-scale fluctuations. It is observed that for large correlation lengths the terms with spatial dispersion are anomalously large. The specific form of these terms is obtained for orientational fluctuations in a nematic and fluctuations of the deformations of the smectic layers in a smectic-A in an orienting magnetic field. It is shown that these effects may be observed optically by means of accurate measurements of the angular dependence of the refractive indices of electromagnetic waves. Zh. éksp. Teor. Fiz. 114, 182–190 (July 1998)     

Slow molecular processes in a nematic liquid crystal confined to random porous network formed by aerosil particles

Frequency dispersion measurements of proton spin–lattice relaxation rates (R ₁) of liquid crystal 4-propyl-4′-pentylazoxybenzene in bulk and confined samples (in random porous network of aerosil nano-particles) are reported in isotropic and nematic phases. Significant low-frequency increase in R ₁ in confined samples indicates slow molecular reorientations mediated by translational displacements near the adsorbing porous surface. The resulting dispersion behavior of R ₁ (～ω ^{? p} ) reflects the nature of the random surface (p?=?0.5 for equi-partition of the diffusive modes). The observed temperature-independent exponent in the isotropic phase (p?=?0.34) indicates the abundance of low-wavelength surface modes. Its temperature-dependent higher values in the nematic phase (from 0.59 to 0.65 on cooling), and increased spin–lattice coupling via this mechanism, show progressive onset of longer wavelength modes. A detailed analysis shows the effect of confinement on the order director fluctuations, molecular reorientations, and translational diffusion of the molecules.