Disclinated states in nematic elastomers

We present a theory for uniaxial nematic elastomers with variable asphericity. As an application of the theory, we consider the time-independent, isochoric radial expansion of a right circular cylinder. Numerical solutions to the resulting differential equation are obtained for a range of radial expansions. For all expansions considered, there exists an isotropic core of material surrounding the cylinder axis where the asphericity vanishes and in which the polymeric chains are shaped as spherical coils. This region, corresponding to a disclination of strength +1 along the axis, is bounded by a narrow transition layer across which the asphericity increases rapidly and attains a non-trivial positive value. The material thereby becomes anisotropic away from the disclination so that the polymeric chains are shaped as ellipsoidal coils of revolution prolate about the cylinder radius. In accordance with the area of steeply changing asphericity between isotropic and anisotropic regimes, a marked drop in the free-energy density is observed. The boundary of the disclination core is associated with the location of this energy drop. For realistic choices of material parameters, this criterion yields a core on the order of 10⁻² μm, which coincides with observations in conventional liquid-crystal melts. Also occurring at the core boundary, and further confirming its location, are sharp transitions in the behavior of the constitutively determined contributions to the deformational stress and a change in the pressure. Furthermore, the constitutively determined contribution to the orientational stress is completely concentrated at the core boundary. The total energy shows a definitive preference for disclinated states.     

Quasiconvex envelopes of energies for nematic elastomers in the small strain regime and applications

We provide some explicit formulas for the quasiconvex envelope of energy densities for nematic elastomers in the small strain regime and plane strain conditions. We then demonstrate their use as a powerful tool for the interpretation of mechanical experiments. Analytical formulas characterizing the stress-strain response in pure shear are derived, providing an easily testable benchmark for future numerical and experimental investigations on the mechanics of nematic elastomers.     

Liquid–crystalline nematic polymers revisited

A new model for nematic polymers is proposed, based on the probability ψ(u,u,t) for a macromolecule to be oriented along direction u while embedded in a u environment created by its neighbours. The potential of the internal forces is written Φ(u,u) accordingly. The free energy contains a contribution ν Φ + k_BT ln ψ where the brackets mean an average over the probability distribution, while ν is the (uniform) polymer number density. An equation is derived for the time-evolution of the order parameter S = uu − I/3, together with an expression for the stress tensor. These two results offer a generalization of the Doi Model in so far as they include a distortional energy, analogue to the Frank elastic energy for low molecular mass nematics. Extending the Maier–Saupe variational procedure, we specify the way that the internal potential Φ(u,u) must be written for it to favour non-zero values of the order parameter, while giving a penalty to situations with gradients of the order parameter. The result is quite different from the potential proposed a decade ago by Marrucci and Greco (their Φ depends on u only), while it has a clear connection with the so-called Landau-de Gennes (LdG) tensor models, which are based on a free-energy depending on the order parameter and its gradients.     

Director reorientation and order reconstruction: competing mechanisms in a nematic cell

We propose a model to explore the competition between two mechanisms possibly at work in a nematic liquid crystal confined within a flat cell with strong uniaxial planar conditions on the bounding plates and subject to an external field. To obtain an electric field perpendicular to the plates, a voltage is imposed across the cell; no further assumption is made on the electric potential within the cell, which is therefore calculated together with the nematic texture. The Landau-de Gennes theory of liquid crystals is used to derive the equilibrium nematic order tensor Q. When the voltage applied is low enough, the equilibrium texture is nearly homogeneous. Above a critical voltage, there exist two different possibilities for adjusting the order tensor to the applied field within the cell: plain director reorientation, i.e., the classical Freedericksz transition, and order reconstruction. The former mechanism entails the rotation of the eigenvectors of Q and can be described essentially by the orientation of the ordinary uniaxial nematic director, whilst the latter mechanism implies a significant variation of the eigenvalues of Q within the cell, virtually without any rotation of its eigenvectors, but with the intervention of a wealth of biaxial states. Either mechanism can actually occur, which yields different nematic textures, depending on material parameters, temperature, cell thickness and the applied potential. The equilibrium phase diagram illustrating the prevailing mechanism is constructed for a significant set of parameters.      

Spinodal decomposition and nematic coarsening in a rigid-rod solution

The dynamics of a solution of rodlike liquid-crystalline molecules are simulated for the related problems of isotropic–nematic spinodal decomposition and the coarsening of misaligned nematic grains. The Doi diffusion equation for the rod distribution function is coupled with the full Onsager intermolecular potential, discretized by the finite-element method, and integrated forward in time by using a parallel, semi-implicit scheme. The Onsager potential models rod interaction on the scale of a single rod length in order to resolve accurately defects and interfaces in structure. Simulation results show the effects of rotational and translational diffusivity ratios on the mechanisms for alignment and phase separation in spinodal decomposition. As rotational motion is restricted, individual grains become more aligned prior to coalescence events. When rods are restricted to diffusive motion along their axis, the spinodal decomposition process is arrested, and the system will reach a pseudo-steady state featuring misaligned nematic grains. These results mark the first dynamic computation of the Doi diffusion equation for spinodal decomposition in nonhomogeneous rigid-rod systems. Nematic coarsening simulations show the effects of misalignment between neighboring ordered domains on the coarsening time and director field around structured interfaces. Results show that the coarsening time is dependent not only on misalignment between grain directors, but also on the tilt angle of the directors into the interface.     

Likelihood and expected-time statistics of monodomain attractors in sheared discotic and rod-like nematic polymers

Employing a mesoscopic Doi tensor model, we develop transient statistical properties of sheared nematic polymer monodomains consistent with typical experimental protocols. Our goal is to convey to the experimentalist a list of expected outcomes, based not only on properties of the nematic liquid and imposed flow rate, but also on the timescale of the experiment and variability in the initial conditions. Step 1 is deterministic: we solve the model equations completely, then compile the flow-phase diagram of all monodomain attractors and phase transitions versus nematic concentration and Peclet number (shear rate normalized by molecular relaxation rate). Step 2 is to overlay on the phase diagram a statistical diagnostic of the expected time, t_A, to reach a small neighborhood of every attractor A. The statistics are taken over the arbitrary quiescent director angle on the sphere, modeling experiments that begin from rest. Step 3 is to explore parameter regimes with multiple attractors, where we statistically determine the likelihood of convergence to each attractor. These statistical properties are critical for any application of theoretical models to the interpretation of experimental data. If t_A is longer than the timescale of the experiment, attractor A is never fully resonated and the relevant stress and scattering predictions are those of the transients, not the attractor. In bi-stable and tri-stable parameter regimes, which are typical of nematic polymers, a distribution of monodomains of each type will populate the sample, so experimental data must be compared with weighted averages based on the likelihood of each attractor (see Grosso et al (2003) Phys Rev Lett 90:098304). The final step is to give statistics of shear stress and normal stress differences during the approach to each attractor type, as well as typical paths of the major director that are contrasted with the results of Van Horn et al (Rheol Acta (2003) 42(6):585–589) with Leslie-Ericksen theory.     

Dynamics of shear aligning of nematic liquid crystal monodomains

The equations of linear and angular momentum for nematic liquid crystals have been described with Ericksen's transversely isotropic fluid [TIF] model and solved for start-up of shear flow at constant rate and varying initial alignment conditions. An analytical solution for the rotation provides predictions of the nematic director which closely agree with experimental results of Boudreau et al. (1999), supporting the validity of Ericksen's TIF model. The solution is limited to flows where the effects of director gradients are negligible. Received: 13 September 1999/Accepted: 24 January 2000     

Landau theory for biaxial nematic liquid crystals with two order parameter tensors

We present a phenomenological theory for the homogeneous phases of nematic liquid crystals constituted by biaxial molecules. We propose a general polynomial potential in two macroscopic order parameter tensors that reproduces the mean-field phase diagram confirmed by Monte Carlo simulations [De Matteis et al. in Phys Rev E 72:041706 (2005)] and recently recognized to be universal [Bisi et al. in Phys Rev E 73:051709 (2006)] for dispersion force molecular pair-potentials enjoying the D _2h symmetry. The requirement that the phenomenological theory comply uniquely with this phase diagram reduces considerably the admissible phenomenological coefficients, both in their number and in the ranges where they can vary.      

The weak shear kinetic phase diagram for nematic polymers

We study the shear problem for nematic polymers as modeled by the molecular kinetic theory of Doi (1981), focusing on the anomalous slow flow regime. We provide the kinetic phase diagram of monodomain (MD) attractors and phase transitions vs normalized nematic concentration (N) and weak normalized shear rate (Peclet number, Pe). We then overlay all rheological features typically reported in experiments: alignment properties, normal stress differences and shear stress. These features play a critical role in the synthesis between theory and experiment for nematic polymers (Larson 1999; Doi and Edwards 1986). MD type is routinely used for rheological shear characterization: cf., flow-aligning 5CB (Mather et al. 1996a), tumbling PBT (Srinivasarao and Berry 1991), and 8CB (Mather et al. 1996b), evidence for a wagging regime (Mewis et al. 1997), out-of-plane kayaking modes (Larson and Ottinger 1991), and evidence for chaotic major director dynamics (Bandyopadhyay et al. 2000). MD transitions correlate with sign changes in normal stresses (Larson and Ottinger 1991; Magda et al. 1991; Kiss and Porter 1978, 1980). Furthermore, structure formation in shear devices appears to be correlated with monodomain precursor dynamics (Tan and Berry 2003; Forest et al. 2002a). In this paper we combine seminal kinetic theory results (Kuzuu and Doi 1983, 1984; Larson 1990; Larson and Ottinger 1991; Faraoni et al. 1999; Grosso et al. 2001), symmetry observations (Forest et al. 2002b), and mesoscopic results on the fate of orientational degeneracy in weak shear (Forest and Wang 2003; Forest et al. 2003a), together with our resolved numerical simulations, to provide the kinetic flow-phase diagram of Doi theory in the weak shear regime, 0<Pe<1, for infinitely thin rods. We report the "birth" of key rheological features at the onset of flow: sign changes and local maxima and minima in normal stress differences (N₁ and N₂) associated with MD transitions. These results serve as the basis for continuation of the kinetic phase diagram to Pe>1 ; as the definitive benchmark for any mesoscopic or continuum model; and experimental data can be compared in order to determine accuracy and limitations of the Doi theory in weak shear.     

Breather-like director reorientations in a nematic liquid crystal with nonlocal nonlinearity

The nature of nonlinear molecular deformations in a homeotropically aligned nematic liquid crystal (NLC) is presented. We start from the basic dynamical equation for the director axis of a NLC with elastic deformations and adopt space curve mapping procedure to analyze the dynamics. The NLC is governed by an integro-differential perturbed nonlocal nonlinear Schrödinger equation and we solve the same using Jacobi elliptic function method aided with symbolic computation and construct an exact solitary wave solution. In order to better understand the effect of nonlocality on the director reorientations of nematic liquid crystal, we have constructed the component forms of director axis using Darboux vector transformation. This intriguing property as a result of the relation between the coherence of the breather-like solitary deformation and the nonlocality reveals a strong need for a deeper understanding in the theory of self-localization in NLC systems.     

Effects of strong anchoring on the dynamic moduli of heterogeneous nematic polymers

We focus on the linear viscoelastic response of heterogeneous nematic polymers to small amplitude oscillatory shear, paying special attention to the macroscopic influence of strong plate anchoring conditions. The model consists of the Stokes hydrodynamic equations with viscous and nematic stresses, coupled to orientational dynamics and structure driven by the flow gradient, an excluded-volume potential, and a two-constant distortional elasticity potential. We show that the dynamical response simplifies when plate anchoring is either tangential or homeotropic, recovering explicitly solvable Leslie–Ericksen–Frank behavior together with weakly varying order parameters across the plate gap. With these plate conditions, we establish “model consistency” so that all experimental driving conditions (plate-controlled velocity [strain] or shear stress, imposed oscillatory pressure) yield identical dynamic moduli for the same material parameters and anchoring conditions, eliminating the culpability of device influence in scaling behavior. Two physical predictions emerge that imply significant macroscopic elastic and viscous effects controlled by plate anchoring relative to flow geometry: (1) The storage modulus is enhanced by two to three orders of magnitude for homeotropic relative to parallel anchoring, across all frequencies. (2) The loss modulus exhibits enhancement of a factor of two to three for homeotropic over tangential anchoring, restricted to low frequencies. We further deduce a scaling law for the dynamic moduli versus anisotropy of the distortional elasticity potential.

Comments on “Breather-like director reorientations in a nematic liquid crystal with nonlocal nonlinearity” by L. Kavitha,M. Venkatesh and D. Gopi

We point out a mistake that the authors of Kavitha et al. (2013) incurred by overlooking the physical meaning of their mathematical derivation. By doing this, we hope to emphasise the importance of an awareness of the strict links which mathematical models need to maintain with physical phenomena and systems.     

A variational formulation for a boundary value problem considering an electro-sensitive elastomer interacting with two bodies

We present a variational formulation for an electro-elastic body in contact with two semi-infinite rigid bodies, which are electric conductors and have a distribution of free charge. These three bodies are surrounded by free space, where far away we have a given electric displacement and an electric potential on disjoint surfaces.     

Superposition principles for small amplitude oscillatory shearing of nematic mesophases

The linear viscoelasticty of Leslie-Ericksen monodomain liquid crystals subjected to a bend distortion through a small amplitude oscillatory shear flow driven by harmonic wall stress is analyzed, using numerical and asymptotic methods. The viscoelastic material functions were derived using a new scaling approach that extracts the material parameters that control superposition. Small and high frequency superposition schemes for linear viscoleasticity were derived. The schemes were successfully applied to collapse the predicted loss and storage linear viscoelastic moduli of seven experimental data sets. Comparisons between different shear flows (simple shear and capillary Poiseuille) and different director distortion modes (splay and bend) shows that the superposition schemes are applicable to shear flows in any single director distortion mode.     

Rheo-dielectric behavior of low molecular weight liquid crystal 2. Behavior of 8CB in nematic and smectic states

Rheo-dielectric behavior was examined for 4−4^′−n-octyl-cyanobiphenyl (8CB) having large dipoles parallel to its principal axis (in the direction of the C≡N bond). In the quiescent state at all temperatures (T) examined, orientational fluctuation of the 8CB molecules was observed as dielectric dispersions at characteristic frequencies ω_c>10⁶ s⁻¹. In the isotropic state at high T, no detectable changes of the complex dielectric constant ɛ^*(ω) were found under slow flow at shear rates ˙γ≫ω_c. In the nematic state at intermediate T, the terminal relaxation intensity of ɛ^*(ω) was decreased under such slow flow. In the smectic state at lower T, the flow effect became much less significant. These results were related to the flow-induced changes of the liquid crystalline textures in the nematic and smectic states, and the differences of the rheo-dielectric behavior in these states are discussed in relation to a difference of the symmetry of molecular arrangements in the nematic and smectic textures. Received: 1 October 1998 Accepted: 13 January 1999     

Free-energy density functions for nematic elastomers

The recently proposed neo-classical theory for nematic elastomers generalizes standard molecular-statistical Gaussian network theory to allow for anisotropic distributions of polymer chains. The resulting free-energy density models several of the novel properties of nematic elastomers. In particular, it predicts the ability of nematic elastomers to undergo large deformations with exactly zero force and energy cost—so called soft elasticity. Although some nematic elastomers have been shown to undergo deformations with unusually small applied forces, not all do so, and none deform with zero force. Further, as a zero force corresponds to infinitely many possible deformations in the neo-classical theory, this non-uniqueness leads to serious indeterminacies in numerical schemes. Here we suggest that the neo-classical free-energy density is incomplete and propose an alternative derivation that resolves these difficulties. In our approach, we use the molecular-statistical theory to identify appropriate variables. This yields the choice for the microstructural degrees of freedom as well as two independent strain tensors (the overall macroscopic strain plus a relative strain that indicates how the deformation of the elastomeric microstructure deviates from the macroscopic deformation). We then propose expressions for the free-energy density as a function of the three quantities and show how the material parameters can be measured by two simple tests. The neo-classical free-energy density can be viewed as a special case of our expressions in which the free-energy density is independent of the overall macroscopic strain, thus supporting our view that the neo-classical theory is incomplete.     

Theory of interfacial dynamics of nematic polymers

 The interfacial momentum and torque balance equations for deforming interfaces between nematic polymers and isotropic viscous fluids are derived and analyzed with respect to shape selection and interfacial nematic ordering. It is found that the interfacial momentum balance equation for nematic interfaces involves bending forces that act normal to the interface, and that interfacial pressure jumps may exist even for planar surfaces. In addition tangential forces on nematic interfaces arise in the presence of surface gradients of the tensor order parameter. The torque balance equation shows that couple stress jumps are balanced by the surface molecular field. The interfacial balance equations are shown to be coupled such that nematic ordering depends on shape and vice versa. The governing dimensionless numbers for deforming nematic polymer interfaces are identified and the limiting regimes are discussed in reference to related experimental data. It is found that the ratio of Frank elasticity to surface anchoring controls whether the surface tensor order parameter deviates from its preferred equilibrium value. Whether the shape is affected, depends on the relative magnitudes of the isotropic surface tension, Frank bulk elasticity, and anchoring energy, and capillary number. Received: 16 April 1999/Accepted: 19 August 1999     

The flow-phase diagram of Doi-Hess theory for sheared nematic polymers II: finite shear rates

The purpose of this paper is to extend the rheological predictions of the Doi-Hess kinetic theory for sheared nematic polymers from the anomalous weak shear regime (Forest et al. 2004a) to arbitrary shear rates, and to associate salient rheological and optical properties with the solution space of kinetic theory. Using numerical bifurcation software (AUTO), we provide the phase diagram of all stable monodomain orientational probability distribution functions (PDFs) and their phase transitions (bifurcations) vs nematic concentration (N) and normalized shear rate (Peclet number, Pe) for Pe1. Shear stresses, normal stress differences, the peak direction of the orientational distribution, and birefringence order parameters are calculated and illustrated for each type of PDF attractor: steady flow-aligning, both in and out of the flow deformation plane and along the vorticity axis; unsteady limit cycles, where the peak orientation direction rotates in-plane or around the vorticity axis or in bi-stable orbits tilted between them; and chaotic attractors first observed in kinetic simulations by Grosso et al. (2001). We pay particular attention to correlations between rheological features and the variety of monodomain phase transitions. Together with the weak flow regime, these results provide a nearly complete picture of the rheological consequences of the Doi-Hess kinetic theory for sheared monodomains of rigid, extreme aspect ratio, nematic rods or platelets.     

Growth and structure of nematic spherulites under shallow thermal quenches

The growth kinetics, shape, interfacial and internal orientation texture of a submicron nematic spherulite arising during the isotropic-to-nematic liquid crystal phase transformation under shallow thermal quenches is analyzed using theory, scaling, and numerical simulations based on the Landau – de Gennes model (The Physics of Liquid Crystals, 2nd edn. Clarendon, Oxford). The numerical computations from this model yield interfacial cusp formation that relaxes through the nucleation of two disclination lines of topological charge +1/2 and subsequently leads to intra-droplet texturing and a net topological charge within the spherulite of +1. The timing of these events suggests that cusp formation at the interface is intimately associated with the interfacial defect shedding mechanism (J. Chem. Phys. 124:244902, 2006) for shallow quenches. These results are different than predictions for deep quenches (J. Chem. Phys. 124:244902, 2006) where interfacial defect shedding leads to four defects and a net topological charge of +2. A liquid crystal dynamic shape equation is derived from the Landau – de Gennes model to account for the interface shape changes in terms of surface viscosity, the driving forces due to the uniaxial nematic-isotropic free energy difference, capillary forces, and friction forces, and used to semi-quantitatively show that during cusp formation and defect shedding, gradient elasticity, capillary forces and friction play significant roles in decelerating and accelerating the surface. An interfacial eigenvalue analysis shows that during the shallow quench, disclination lines nucleate within the interface itself and then texturize the nematic droplet as they migrate from within the interface to the bulk of the growing nematic droplet. After defect shedding, the spherulite is nearly circular and grows with constant velocity, in agreement with experiments. The results shed new light on intra-spherulite texturing mechanisms in phase ordering under weak driving forces.