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     

Induced ferrielectricity in antiferroelectric liquid crystals

The behaviour of the antiferroelectric SmC_A liquid crystal phase under applied electric field is discussed theoretically. The phase diagram involving the SmA, SmC_A and SmC _A ^* phases is worked out and shown to exhibit a Lifshitz critical point. The deformation of the bilayer structures induced by the field transforms the SmC_A phases into a ferrielectric phase whose specific configuration is described. Received: 23 October 1997 / Revised: 8 April 1998 / Accepted: 14 July 1998     

Phases hexagonales colonnaires thermotrope et lyotrope : défauts observés par cryofracture et caractère anomal du thermotrope

Electron microscopy observations of replicas of freeze-fractured samples of two columnar hexagonal phases of different nature (a lyotropic one, the inverse AOT in water; a thermotropic one, ) yield very different results: most defects at microscopic scales are screw dislocations in the lyotropic phase, longitudinal edge dislocations in the thermotropic phase. A possible way to interpret these differences is as follows: in the lyotropic the Lamé coefficients and μ and the bend modulus K₃ would not display any anomaly compared to expected values; in the thermotropic the shear modulus μ would be ten times smaller than the compressibility modulus , while K₃ would still be comparable to (but larger than) the bend modulus of a small molecules liquid crystal. We present an elementary theoretical model of the latter case which could explain the anomalous measurements of K₃ and of the longitudinal compressibility (Ref. [#!ref10!#]) without contradicting more recent measurements of (Refs. [#!ref17!#,#!ref22!#]). Essentially, the hexagonal phase would be a phase with defects (longitudinal dislocations) akin to an hexatic phase but with some differences. Re?u : 26 mai 1997 / Révisé : 20 Janvier 1998 / Accepté : 27 avril 1998     

Stability of the director profile of a nematic liquid crystal around a spherical particle under an external field

We study numerically the effect of an external magnetic or electric field on the director profiles of a nematic liquid crystal around a spherical particle. We pay particular attention to the stability of a hyperbolic hedgehog defect accompanying the particle, which transforms into a Saturn-ring defect encircling the particle under a sufficiently strong external field. We focus on the particle size dependence of the two important threshold field strengths: the “thermodynamic-transition” field strength H₁ at which the hedgehog and the Saturn-ring configurations have the equal free energy, and the critical field strength H₂ at which the hedgehog loses its (meta)stability. Our numerical results demonstrate that while H₁ is non-monotonically dependent on the particle radius R₀, H₂ monotonically increases with R₀ and the dependence of H₂ is weak for large R₀. The non-monotonic dependence of H₁ on R₀ can be explained by comparing the energies of the two configurations and assuming the dependence of those energies on a rescaled field. A crude argument of the energetics of a hyperbolic hedgehog defect under an external field shows that for an asymptotically large R₀ the critical field strength is independent of R₀, which agrees with our numerical finding.     

Universal non-monotonic smectic fluctuations of liquid crystal films in a magnetic field

Free-standing liquid crystal films with positive diamagnetic susceptibility can have the smectic ordering enhanced by an external field applied perpendicular to the plane layers. Within a quadratic functional integral approach, we investigate the interplay between the smectic order induced by an external field H and that due to the surface tension γ between the film and the surrounding gas. We find that the average smectic fluctuation is a non-monotonic function of film thickness, with a characteristic thickness scale ξ _H delimiting the predominance of surface tension and magnetic field effects. This characteristic thickness obeys simple asymptotic power-law relations as a function of the ordering terms which allows us to represent the average smectic fluctuations in a universal scaling form. Received 7 January 2003 Published online 1st April 2003 RID="a" ID="a"e-mail: marcelo@ising.fis.ufal.br     

Smectic-A edge dislocations in a very thin cell

We study stable “bookshelf” smectic-A structures within a very thin plane-parallel cell of thickness L in which the mismatch between surface preferred (d _s) and intrinsic (d₀) smectic layer thicknesses occurs. The Landau-Ginzburg approach based on a complex smectic order parameter is used. For a weak enough smectic positional anchoring strength W smectic layers adopt the modified bookshelf profile. In a thick enough cell with increasing W a lattice of edge dislocations is continuously formed at the confining surfaces and then depinned from them. The structure with dislocations is formed when the condition d ₀/( d ₀/d _s - 1) ∼ 2 is fulfilled, where is the positional surface anchoring extrapolation length. If the cell is thin enough the dislocations formed at opposite cell plates annihilate and consequently the smectic layers adopt a locked bookshelf structure. This transition is discontinuous and takes place when d ₀/(L d ₀/d _s - 1) ∼ 5 is realized. To observe these transitions in a cell of thickness L∼ 1μm the conditions W∼ 10^-6 J/m ² and d ₀/d _s - 1∼ 5 ^. 10^-4 have to be fulfilled. All the three qualitatively different structures coexist at the triple point. Received 21 February 2002     

Structure and rheology of concentrated wormlike micelles [4]at the shear-induced isotropic-to-nematic transition

We have investigated the simple shear flow behavior of wormlike micelles using small-angle neutron scattering and mechanical measurements. Ternary surfactant solutions made of cetylpyridinium chloride, hexanol and brine (0.2 M NaCl) and hereafter abbreviated as CPCl-Hex were studied in the concentrated regime, . In a preliminary report (Berret et al. [#!ref16!#]), the discontinuity of slope observed in the shear stress versus shear rate curve was interpreted in terms of first-order phase transition between an isotropic state and a shear-induced nematic state ( transition). At the transition rate, , the solution exhibits a macroscopic phase separation into viscous and fluid layers (inhomogeneous shear flow). Above a second characteristic shear rate, the flow becomes homogeneous again, the sheared solution being nematic only. The neutron patterns obtained in the two-state inhomogeneous region have been re-examined. Based on a consistent analysis of both orientational and translational degrees of freedom related to the wormlike micelles, we emphasize new features for the transition. In the present paper, the shear rate variations of the relative proportions of each phase in the two-state region, as well as the viscosity ratio between isotropic and nematic phases are derived. We demonstrate in addition that slightly above the transition rate, the shear induced nematic phase is already strongly oriented, with an order parameter P ₂ = 0.65. The orientational state is that of a nematic flow-oriented monodomain. Finally, from the locations of the neutron scattering maxima for each isotropic and nematic contributions, we evaluate the concentrations for each phase and and derived a dynamical phase diagram of CPCl-Hex, in terms of the stress versus and . According to the classification by Schmitt et al. [#!ref22!#], the transition observed in CPCl-Hex micellar solutions could result from a positive flow-concentration coupling, in agreement with the observed monotonically increasing shear stress in the two-phase region. Received: 16 February 1998 / Revised: 18 February 1998 / Accepted: 24 May 1998     

Effect of high electric fields on the nematic to isotropic transition in a material exhibiting large negative dielectric anisotropy

We report the experimental high electric field phase diagram of a nematic liquid crystal which exhibits a large negative dielectric anisotropy. We measure simultaneously the birefringence (Δn) and the dielectric constant (epsilon_⊥) at various applied fields as functions of the local temperature of an aligned sample. We also measure the higher harmonics of the electrical response of the medium. The following experimental results are noted: (i) enhancement of orientational order parameter S in the nematic phase due to both the Kerr effect and quenching of director fluctuations; (ii) enhancement in the paranematic to nematic transition temperature (T_PN) with field; (iii) divergence of the order parameter susceptibility beyond the tricritical point as measured by third harmonic electrical signal; (iv) a small second harmonic electrical signal which also diverges near T_PN, indicating the presence of polarised domains. Our measurements show that ΔT_PN(= T_PN(E)-T_NI(0)) varies linearly with |E| whereas the Landau de Gennes theory predicts a dependence on E². It is argued that the quenching of director fluctuations by the field makes the dominant contribution to all the observations, including the thermodynamics of the transition.     

Tilted smectic layers of a liquid crystal between homeotropically treated plates

We investigated SmC^* films sandwiched between silane coated glass plates and observed formation of textures exhibiting a uniform tilt of the smectic layers with respect to the boundary plates. The layer tilt angle increases from zero to as the sample is cooled from the smectic A phase to room temperature. These films show linear electro-optical effects because the permanent polarization can be aligned so that it has a component parallel to the applied field without changing the layer structure. Our analysis indicates that mainly two effects determine the layer tilt. On the one hand, the surface tension tends to minimise the layer tilt. On the other hand, the surface energy promotes the director to be normal to the boundary plates. Received 17 July 1998     

Configuration of a chiral smectic-C film with a circular inclusion

It was shown experimentally (P.V. Dolganov et al., Europhys. Lett. 76, 250 (2006)) and by numerical calculations (C. Bohley, R. Stannarius, Eur. Phys. J. E 23, 25 (2007)) that the c -director profile of a two-dimensional chiral smectic-C (SmC) film around a circular inclusion adopts dipolar rather than quadrupolar configuration observed in achiral SmC films. We give an analytical argument on how spontaneous bend inherent in chiral SmC liquid crystals influences the configuration of a SmC liquid crystal film around a circular inclusion imposing tangential anchoring. We find how the angle α between two surface defects seen from the center of the inclusion depends on the radius of the inclusion R and the strength of the spontaneous bend q . We show, however, that the contribution of the spontaneous bend to the free energy suffers from mathematical ambiguity; it depends on the mathematical treatment of the outer boundary even when it is at infinity. This might indicate that the shape as well as the treatment of the outer boundary of the film can significantly influence the equilibrium configuration of the c -director and the position of the surface defects.     

Nematic ordering in anisotropic elastomers: Effect of frozen anisotropy

Nematic ordering in anisotropic non-Gaussian elastomers is considered theoretically using mean field approximation. We focus on the effect of anisotropy during network cross-linking on the system elasticity and, in particular, on the so-called soft deformation mode. As the main result, we calculate the dependence of the elastomer free energy on the angle between the axis of “frozen” anisotropy and the nematic director. The dependence of the isotropic-nematic transition point on the orientational field acting on the monomers during the cross-linking process is also calculated. Received: 5 November 1997 / Revised and Accepted: 29 June 1998     

Theoretical investigations of rotational phenomena and dielectric properties in a nematic liquid crystal

The molecular dynamics (MD) simulation, based on a realistic atom-atom interaction potential, was performed on 4-n-pentyl-4'-cyanobiphenyl (5CB) in the nematic phase. The rotational viscosity coefficients (RVCs) γ _i, (i = 1, 2) and the ratio of the RVCs λ = - γ ₂/γ ₁ were investigated. Furthermore, static and frequency-dependent dielectric constants and ε were calculated using parameters obtained from the MD simulation. Time correlation functions were computed and used to determine the rotational diffusion coefficient, D _⊥. The RVCs and λ were evaluated using the existing statistical-mechanical approach (SMA), based on a rotational diffusion model. The SMA rests on a model in which it is assumed that the reorientation of an individual molecule is a stochastic Brownian motion in a certain potential of mean torque. According to the SMA, γ _i are dependent on the orientational order and rotational diffusion coefficients. The former was characterized using: i) orientational distribution function (ODF), and ii) a set of order parameters, both derived from analyses of the MD trajectory. A reasonable agreement between the calculated and experimental values of γ _i and λ was obtained. Received 22 March 2000 and Received in final form 8 October 2000     

Using the full Raman depolarisation in the determination of the order parameters in liquid crystal systems

The depolarisation ratio for the Raman-active phenyl stretching mode has been measured over the whole of the mesophase range, and the orientational order parameters deduced, in the uniaxial nematic liquid crystal octylcyanobiphenyl (8CB). Linearly polarised light was incident normally on a homogeneously aligned sample and a χ² minimisation routine performed on the 360^° depolarisation ratio profile. The order parameters 〈P ₂₀₀〉 and 〈P ₄₀₀〉 , together with the differential polarisability ratio, r , are used as fitting parameters and measured as a function of temperature. Interestingly, we show that the value for r , conventionally measured in the isotropic phase and assumed to remain constant, has a clear temperature dependence, ranging from -0.032±0.008 in the isotropic phase through to -0.245±0.015 at the nematic-to-smectic A phase transition. The measured order parameters 〈P ₂₀₀〉 and 〈P ₄₀₀〉 varied from 0.35- 0.55±0.02 and 0.180- 0.245±0.02 , respectively, across the 8 ^° C wide nematic phase range. The values of both 〈P ₂₀₀〉 and 〈P ₄₀₀〉 are in excellent agreement with theory, but it is noteworthy that 〈P ₄₀₀〉 shows a much better quantitative match than has been reported in previous work. Crucially the temperature dependence of r is shown to be a contributing factor in the low 〈P ₄₀₀〉 values that have been conventionally reported from Raman scattering measurements. The potential for fitting the entire angular depolarisation ratio distribution in liquid crystalline systems that are described by more order parameters, specifically biaxial materials, is discussed.     

Lamellar-to-nematic phase transition in a lipid-surfactant mixture

A lyotropic system, consisting of a lecithin (DMPC) and a non-ionic surfactant (C₁₂E₅) in water was studied. The system exhibits a lamellar-to-nematic phase transition. The nematic phase appears as the temperature is decreased and only exists in a very limited temperature and concentration range, for specific lipid-to-surfactant ratios. While a lamellar phase is found at higher temperatures in both mixed and pure C₁₂E₅ systems, the transition to the nematic phase at lower temperatures coincides with a micellar phase in the pure C₁₂E₅ system. The transition appears to be driven by the strong temperature dependence of the surfactant film spontaneous curvature. The structural properties of the lamellar phase close to the lamellar-to-nematic boundary have been studied by polarised light microscopy and small-angle neutron and X-ray scattering experiments. The signature of a helical defect with Burgers vector of magnitude 2 is apparent in our data, close to the lamellar-to-nematic phase transition. The proliferation of screw dislocations in the lamellar phase might be a plausible mechanism for driving this transition. Received 6 July 1999 and Received in final form 17 April 2000     

Switching of banana liquid crystal mesophases under field

Taking advantage of the great number of bent-core or “banana" compounds synthesized and studied in the laboratory, we describe their behaviour under the application of an external electric field. If the field were a static one, we would work within the frame of an equilibrium phase diagram in a (field E, temperature T) space where some phases would be simple dielectrics and others ferroelectric ones with a macroscopic polarization, either spontaneous or induced by the field. In this paper, we deal with the basic responses of “banana” liquid crystals under the application of a low frequency (1 to 100 Hz) AC field. Firstly square-wave voltages allow us to locate the phase boundary between dielectric (at lower field) and ferroelectric phases (higher field) at a given temperature and field threshold. Then we apply slowly varying AC voltages with shapes like triangle or “triple-plateau” to check out the stability of the induced ferroelectric phase versus field removal. Three behaviours are encountered, the unstable one (short lifetime of the high-field ferroelectric phase) where the macroscopic polarization is destroyed and then rebuilt in the opposite direction during each half period and usually called “antiferroelectric”; the stable one (long lifetime) with a polarization that rotates at constant modulus which is labeled as “ferroelectric” and a new one where the macroscopic polarization is proportional to the applied fied, we named this behaviour as “superparaelectric”. Let us stress that these observations apply to the ferroelectric phases of the (E, T) phase diagram not to the zero field (0,T) phases observed in the usual phase characterization experiments except for an eventual spontaneous ferroelectric phase. Received 18 April 2002 and Received in final form 17 January 2003 Published online: 16 April 2003 RID="a" ID="a"e-mail: marcerou@crpp.u-bordeaux.fr RID="b" ID="b"URL: http://www.crpp-bordeaux.cnrs.fr     

Steps and facets at the surface of soft crystals

We consider the shape of crystals which are soft in the sense that their elastic modulus μ is small compared to their surface tension γ, more precisely μa < γ where a is the lattice spacing. We show that their surface steps penetrate inside the crystal as edge dislocations. As a consequence, these steps are broad with a small energy which we calculate. We also calculate the elastic interaction between steps a distance d apart, which is a 1/d ² repulsion. We finally calculate the roughening temperatures of successive facets in order to compare with the remarkable shapes of lyotropic crystals recently observed by Pieranski et al. [#!Pieranski!#,#!EPJ!#]. Good agreement is found. Received 25 June 2001     

Line defect dynamics around a colloidal particle

We study experimentally the dynamics of a topological defect located around a colloidal particle suspended in a thermotropic nematic liquid crystal. The considered defect consists of a disclination loop encircling the particle at the equator. Under specific conditions, it is shown that this disclination continuously shrinks to a hedgehog defect located in the immediate vicinity of the particle. This phenomenon corresponds to a transition between an elastic quadrupolar configuration and an elastic dipolar configuration. We performed a basic numerical calculation to get an estimate of the dissipated energy during the transition; we compare the results with theoretical predictions that describe the elastic energy of particles surrounded by defects. Received 21 December 2001     

Reaction kinetics in polymer melts

We study the reaction kinetics of end-functionalized polymer chains dispersed in an unreactive polymer melt. Starting from an infinite hierarchy of coupled equations for many-chain correlation functions, a closed equation is derived for the 2nd order rate constant k after postulating simple physical bounds. Our results generalize previous 2-chain treatments (valid in dilute reactants limit) by Doi [#!doi:inter2!#], de Gennes [#!gennes:polreactionsiandii!#], and Friedman and O'Shaughnessy [#!ben:interdil_all_aip!#], to arbitrary initial reactive group density n₀ and local chemical reactivity Q. Simple mean field (MF) kinetics apply at short times, .For high Q, a transition occurs to diffusion-controlled (DC) kinetics with (where x_t is rms monomer displacement in time t) leading to a density decay . If n₀ exceeds the chain overlap threshold, this behavior is followed by a regime where during which k has the same power law dependence in time, , but possibly different numerical coefficient. For unentangled melts this gives while for entangled cases one or more of the successive regimes ,t ^-3/8 and t ^-3/4 may be realized depending on the magnitudes of Q and n₀. Kinetics at times longer than the longest polymer relaxation time are always MF. If a DC regime has developed before then the long time rate constant is where R is the coil radius. We propose measuring the above kinetics in a model experiment where radical end groups are generated by photolysis. Received: 2 June 1998 / Revised: 9 July 1998 / Accepted: 10 July 1998     

Magnetization dynamics below of EuO and EuS

Between 4.2 K and the Curie temperatures of the cubic Heisenberg ferromagnets EuS and EuO, their homogeneous dynamic susceptibilities have been investigated by means of a broad-band reflectometer operating from 0.1 GHz to 40 GHz. For internal magnetic fields larger than the anisotropy fields H A ( T ) of both materials, their static susceptibilities exhibit a -divergence, which reveals quantitatively the dominance of dipolar-anisotropic spin-wave fluctuations. displays a Lorentzian shape the damping frequency of which obeys scaling in terms of .The scaling function agrees quantitatively with work by Frey and Schwabl [#!FS88!#] for dipolar Heisenberg ferromagnets at temperatures above T_c. Building upon their approach, the resonance frequency of the Lorentzian can be related to a memory effect in the damping determined by the large value of the relaxation rate of the longitudinal magnetization fluctuations . For EuS, this relation is substantiated directly by inelastic neutron scattering. All these features reveal the hitherto uncovered importance of the dipolar anisotropic fluctuations below T_c of ferromagnets. Received: 4 March 1998 / Accepted: 12 May 1998