Biaxial liquid-crystal elastomers: A lattice model

We present a simple coarse-grained lattice model for monodomain biaxial liquid-crystal elastomers and perform large-scale Monte Carlo simulations in the proposed model system. Orientational ordering --uniaxial or biaxial-- reflects in sample deformations on cooling the system. The simulation output is used to predict calorimetry data and deuterium magnetic resonance spectra.     

Critical voltages and blocking stresses in nematic gels

We present a model of the dynamics of director rotation in nematic gels under combined electro-mechanical loading. Focusing on a model specimen, we describe the critical voltages that must be exceeded to achieve director reorientation, and the blocking stresses that prevent alignment of the nematic director with the applied electric field. The corresponding phase diagram shows that the dynamic thresholds defined above are different from those predicted on the sole basis of energetics. Multistep loading programs are used to explore the energy landscape of our model specimen, showing the existence of multiple local minima under the same voltage and applied stress. This leads us to conclude that hysteresis should be expected in the electro-mechanical response of nematic gels.     

Dynamics of reorientation of a constrained nematic elastomer

A model is proposed for the reorientation dynamics of a confined nematic liquid crystal elastomer, where the effect of crosslinks is to couple the director to deformations of the elastic matrix. The model combines the (equilibrium) `neo-classical' theory of liquid crystal rubber elasticity with the simplest time evolution equations for a system described by two coupled, non-conserved order parameters. Relaxation from an orientation imposed by an electric field is studied as a function of elastic softness, starting angle, surface pretilt, and the relative mobilities of director and strain. Most importantly, the absence of a `semi-soft' elastic threshold changes the long-time behaviour of the effective refractive index of the medium from exponential to inverse power law decay. Predictions are compatible with recent experimental results by Chang, Chien and Meyer [Phys. Rev. E 56, 595 (1997)]. Received 22 June 1998     

Phase transition in liquid crystal elastomers—A Monte Carlo study employing non-Boltzmann sampling

We investigate nematic-isotropic transition in liquid crystal elastomers employing a variant of Wang-Landau sampling. This technique facilitates calculation of the density of states from which other thermodynamic properties can be obtained. We consider a lattice model of a liquid crystal elastomer and a Hamiltonian which accounts for interactions among liquid crystalline units and interaction of local nematics with global strain. We investigate the effect of varying the strength of coupling between nematic and orientational degrees of freedom. When the local director is coupled strongly to the global strain, the transition is strongly first order. When the strength of the coupling decreases the transition becomes weakly first order. The transition temperature decreases when the coupling becomes weaker. We also report for the first time results on variation of free energy as a function of average energy at different temperatures and coupling constants.     

Piezoelectricity of chiral nematic elastomers

A molecular model of freely jointed chains of chiral monomers is developed to describe the piezoelectric effect in chiral nematic elastomers. The model, an extension of the neo-classical theory of nematic polymer networks, takes into account a chiral biasing of molecular alignment under shear which leads to induced polarisation if the monomers contain a transverse dipole moment. The resulting theory is fully non-linear in elastic deformations, in the spirit of ordinary rubber elasticity. The expansion to the highest order in small strains gives the three linear piezoelectric coefficients predicted by phenomenological models. Received 7 September 1998 and Received in final form 19 October 1998     

Tube model for the elasticity of entangled nematic rubbers

Dense rubbery networks are highly entangled polymer systems, with significant topological restrictions for the mobility of neighbouring chains and crosslinks preventing the reptation constraint release. In a mean-field approach, entanglements are treated within the famous reptation approach, since they effectively confine each individual chain in a tube-like geometry. We apply these classical ideas to calculate the effective rubber-elastic free energy of anisotropic networks, nematic liquid crystal elastomers, and present the first theory of entanglements for such a material. Received 25 June 2001     

Linear hydrodynamics and viscoelasticity of nematic elastomers

We develop a continuum theory of linear viscoelastic response in oriented monodomain nematic elastomers. The expression for the dissipation function is analogous to the Leslie-Ericksen version of anisotropic nematic viscosity; we propose the relations between the anisotropic rubber moduli and new viscous coefficients. A new dimensionless number is introduced, which describes the relative magnitude of viscous and rubber-elastic torques. In an elastic medium with an independently mobile internal degree of freedom, the nematic director with its own relaxation dynamics, the model shows a dramatic decrease in the dynamic modulus in certain deformation geometries. The degree to which the storage modulus does not altogether drop to zero is shown to be both dependent on frequency and to be proportional to the semi-softness, the non-ideality of a nematic network. We consider the most interesting geometry for the implementation of the theory, calculating the dynamic response to an imposed simple shear and making predictions for effective moduli and (exceptionally high) loss factors. Received 16 October 2000 and Received in final form 10 December 2000     

Dielectric properties of side chain liquid crystalline elastomers: influence of crosslinking on side chain dynamics

Dielectric response, from 1 Hz to 10 MHz, of liquid crystalline side chain elastomers has been compared to the one of analogous uncrosslinked materials. Results are discussed in terms of mobility of the mesogens. Two different systems have been investigated: smectic A elastomers allow to determine the influence of crosslinking on the relaxation (i.e. the reorientation of the whole mesogen around the chain), a S _C ^* elastomer shows the drastic influence of the polymer network on the Goldstone mode. Received 12 October 1998     

A dissipative particle dynamics study of the realignment of a nanodroplet of a nematic in a weak external magnetic field

We present a dissipative particle dynamics (DPD) approach for simulating the realignment of a nematic nanodroplet suspended in an isotropic fluid following a switch in the direction of an applied external magnetic field. The interaction of the mesogens with the external field is weak relative to the inter-molecular interactions. The simulations were used to investigate the way orientational equilibrium is re-established. The results reveal that the realignment process of the nanodroplet is consistent with its fluid structure. The reorientation of the nanodroplet as a whole is found to be caused by an internal structural rearrangement rather than a coherent rotation of the centres of mass of the mesogens about the centre of the nanodroplet. The switch in the field direction furthermore is found to induce a transient spatial variation in the orientational order of the long axes of the mesogens: the orientational order parameters decreases on moving from the core of the nanodroplet to the surface in contact with the isotropic environment. The results highlight differences between the time evolution of the orientation of the long molecular axes in the field and the rotations of the centres of mass of the mesogens about the centre of the nanodroplet.     

Spontaneous thermal expansion of nematic elastomers

We study the monodomain (single-crystal) nematic elastomer materials, all side-chain siloxane polymers with the same mesogenic groups and crosslinking density, but differing in the type of crosslinking. Increasing the proportion of long di-functional segments of main-chain nematic polymer, acting as network crosslinking, results in dramatic changes in the uniaxial equilibrium thermal expansion on cooling from the isotropic phase. At higher concentration of main chains their behaviour dominates the elastomer properties. At low concentration of main-chain material, we detect two distinct transitions at different temperatures, one attributed to the main-chain, the other to the side-chain component. The effective uniaxial anisotropy of nematic rubber, r(T) = / proportional to the effective nematic order parameter Q(T), is given by an average of the two components and thus reflects the two-transition nature of thermal expansion. The experimental data is compared with the theoretical model of ideal nematic elastomers; applications in high-amplitude thermal actuators are discussed in the end. Received 25 June 2001 and Received in final form 29 September 2001     

Annihilation of nematic point defects: Pre-collision and post-collision evolution

The annihilation of the nematic hedgehog and anti-hedgehog within an infinite cylinder of radius R is studied. The semi-microscopic lattice-type model and Brownian molecular dynamics are used. We distinguish among the i) early pre-collision, ii) late pre-collision, iii) early post-collision, and iv) late post-collision stages. In the pre-collision stage our results agree qualitatively with the existing experimental observations and also continuum-type simulations. The core of each defect exhibits a ring-like structure, where the ring axis is set perpendicular to the cylinder symmetry axis. For ξ⁽⁰⁾_d/(2R) > 1 the interaction between defects is negligible, where ξ⁽⁰⁾_d describes the initial separation of defects. Consequently, the defects annihilate within the simulation time window for ξ⁽⁰⁾_d/(2R) < 1. For close enough defects their separation scales as ξ_d (t_c - t)^0.4±0.1, where t_c stands for the collision time. In elastically anisotropic medium the hedgehog is faster than the anti-hedgehog. In the early pre-collision stage the defects can be treated as point-like particles, possessing inherent core structure, that interact via the nematic director field. In the late pre-collision stage the cores reflect the interaction between defects. After the collision a charge-less ring structure is first formed. In the early post-collision stage the ring adopts an essentially untwisted circular structure of the radius ξ_r. In the late post-collision stage we observe two qualitatively different scenarios. For μ = ξ_r/R < μ_c ∼ 0.25 the ring collapses leading to the escaped radial equilibrium structure. For μ > μ_c the chargeless ring triggers the nucleation growth into the planar polar structure with line defects.     

The flexoelectric effect in nematic liquid crystals: A statistical- mechanical approach

The flexoelectric coefficients e₁ and e₃ for polar liquid crystals, such as 4-n-pentyl- 4^′-cyanobiphenyl, are investigated theoretically by means of an integral equation approach, which takes into account translational, orientational correlations as well as their coupling. e₁ and e₃ are evaluated from microscopic expressions derived on the basis of a density-functional method. Received 27 April 2001 and Received in final form 27 August 2001     

Segmental order in end-linked polymer networks: A Monte Carlo study

Segmental order in end-linked monomodal and bimodal polymer networks is investigated by means of bond-fluctuation Monte Carlo simulations. The tensor order parameter, which is a central observable in NMR experiments, is not uniquely related to simple vectorial order. The relaxation of NMR-detected tensorial interactions towards their finite long-time limit is best described by a power law and occurs over much longer time scales than the relaxation of vectorial order. The well-known prediction for the segmental order of Gaussian chains as a simple function of the segment number between constraints is not straightforwardly obeyed, neither in dry nor in swollen networks. Excluded-volume interactions tend to significantly reduce the tensorial order, as is clearly observed in single-chain simulations. A distribution extends along the chain, where order is increased in a region of 30-40 bonds around the cross-links in networks. The dominating contribution to the order parameter distribution arises from the frozen-in distribution of end-to-end separations. We find strong deviations from the Gamma distribution, which has so far been implicitly used in most NMR works, as it is a straightforward consequence of a Gaussian distribution of end separations. Specifically, we find narrower distributions, as small values of the tensor order parameter are strongly suppressed, most probably as a result of trapped entanglements. The markedly subaffine behavior of the average order parameter and the changes in its distribution on swelling are assigned to orientation processes of strands which compensate for the non-affine local deformation. Our central observations and interpretations are well supported by our previous experimental and theoretical work.     

Instabilities in nematic elastomers in external electric and magnetic fields

In this paper we study the macroscopic behavior of nematic side-chain liquid single crystal elastomers exposed to an external electric or magnetic field. For this purpose we use the framework of a continuum model. The geometries investigated comprise the bend and the twist geometry known from the classical Frederiks transition in low molecular weight liquid crystals. For the bend geometry we find a laterally homogeneous and a two-dimensional undulatory instability, which may compete at onset. In the case of the twist geometry three instabilities can occur at onset, two of which are two dimensional and clearly show undulations. As a major result we propose how the values of the twist coefficient K(2) and the values of the material parameters D(1) and D(2) connected to relative rotations between the director field and the polymer network can be determined from experimental observations. In addition, we explain why a twist experiment is probably the most suitable set-up in order to measure the material parameter D(1).     

Orientational phase transition and the solvation force in a nematic liquid crystal confined between inhomogeneous substrates

A nematic liquid crystal confined between two identical flat solid substrates, with an alternating stripe pattern of planar and homeotropic anchoring, is studied in the framework of the Frank-Oseen theory. By means of numerical minimization of the free energy functional we study the effect of the sample thickness D on the location of the phase transition between a uniform alignment, either planar or homeotropic, and a distorted nematic texture. The solvation force f due to distortions of the nematic director is also studied. It is found that f is always attractive, and for D small compared to the periodicity of the surface structure it exhibits two distinct asymptotic behaviors: f ∼ - D ^-1/2 or f ∼ - D ^-1, depending on the relation between D and the extrapolation lengths. Received 12 November 2002 Published online: 16 April 2003     

Effect of shape anisotropy on the phase diagram of the Gay-Berne fluid

We have used the density functional theory to study the effect of molecular elongation on the isotropic-nematic, isotropic-smectic A and nematic-smectic A phase transitions of a fluid of molecules interacting via the Gay-Berne intermolecular potential. We have considered a range of length-to-width parameter 3.0 ⩽ x₀ ⩽ 4.0 in steps of 0.2 at different densities and temperatures. Pair correlation functions needed as input information in density functional theory are calculated using the Percus-Yevick integral equation theory. Within the small range of elongation, the phase diagram shows significant changes. The fluid at low temperature is found to freeze directly from isotropic to smectic A phase for all the values of x₀ considered by us on increasing the density while the nematic phase stabilizes in between isotropic and smectic A phases only at high temperatures and densities. Both isotropic-nematic and nematic-smectic A transition density and pressure are found to decrease as we increase x₀. The phase diagram obtained is compared with computer simulation result of the same model potential and is found to be in good qualitative agreement.     

Structure and elastic properties of a nematic liquid crystal: A theoretical treatment and molecular dynamics simulation

The Frank elasticity constants which describe splay (K ₁), twist (K ₂), and bend (K ₃) distortion modes are investigated for 4-n-pentyl-4'-cyanobiphenyl (5CB) in the nematic liquid crystal. The calculations rest on statistical-mechanical approaches where the absolute values of K _i (i=1,2,3) are dependent on the direct correlation function (DCF) of the corresponding nematic state. The DCF was determined using the pair correlation function by solving the Ornstein-Zernike equation. The pair correlation function, in turn, was obtained from molecular dynamics (MD) trajectory. Three different approaches for calculations of the elasticity constants were employed based on different level of approximation about the orientational order and molecular correlations. The best agreement with experimental values of elasticity constants was obtained in a model where the full orientational distribution function was used. In addition we have investigated the approximation about spherical distribution of the intermolecular vectors in the nematic phase, often used in derivation of various mean-field theories and employed here for the construction of the DCF. We found that this assumption is not strictly valid, in particular a strong deviation from the isotropic distribution is observed for short intermolecular distances. Received 22 March 2000 and Received in final form 9 June 2000     

Effect of aerosil dispersions on the nematic-to-isotropic interface

The effect of silica aerosils on the kinetics of the first-order nematic-isotropic (NI) phase transition is phenomenologically described in the framework of the time-dependent Landau-Ginzburg equation. A steady-state solution to the equation is presented such that the NI interface may propagate with a solitary-like wave profile under constant quenching. The results provide a plausible basis for the interpretation of the dynamical effects of quenched disorder in the liquid-crystal systems, caused by randomly interconnected porous media, such as aerosils. In the low silica aerosil ρ_s ( ≤0.1 g/cm^3) regime, the calculated values of the interface velocity v(T,ρ_s), the interface thickness κ(T,ρ_s), and the critical radius of a spherical nucleus of new nematic phase in a bulk isotropic environment, composed of polar molecules, such as 4-n-octyl- 4^′- cyanobiphenyl and 4-n-heptyl- 4^′- cyanobiphenyl shows that the effect of silica aerosils on the kinetics is reflected in a shifting of the set of temperature-dependent curves to lower temperature values.-1     

Water droplets in a spherically confined nematic solvent: A numerical investigation

Recently, it was observed that water droplets suspended in a nematic liquid crystal form linear chains [Poulin et al., Science 275, 1770 (1997)]. The chaining occurs, e.g., in a large nematic drop with homeotropic boundary conditions at all the surfaces. Between each pair of water droplets a point defect in the liquid crystalline order was found in accordance with topological constraints. This point defect causes a repulsion between the water droplets. In our numerical investigation we limit ourselves to a chain of two droplets. For such a complex geometry we use the method of finite elements to minimize the Frank free energy. We confirm an experimental observation that the distance d of the point defect from the surface of a water droplet scales with the radius r of the droplet like .When the water droplets are moved apart, we find that the point defect does not stay in the middle between the droplets, but rather forms a dipole with one of them. This confirms a theoretical model for the chaining. Analogies to a second order phase transition are drawn. We also find the dipole when one water droplet is suspended in a bipolar nematic drop with two boojums, i.e., surface defects at the outer boundary. Finally, we present a configuration where two droplets repel each other without a defect between them. Received 11 December 1998