Existence, stability and structure of a hexagonal phase doped with nanoparticles

We describe and study by small-angle X-ray scattering (SAXS) a new type of hybrid system. It is composed of a swollen lyotropic hexagonal phase into the cylinders of which solid magnetic particles of nanometric size have been incorporated. It has been found to be stable for volume fractions of particles up to 2% provided the cylinders are sufficiently large. A unidimensionnal magnetic liquid is thus realized. The structural properties of this colloidal assembly have been investigated by SAXS, and the specific features of the scattering spectra are analysed and interpreted. One of the remarkable results is the evidence of depletion interactions between the particles and the inner walls of the cylinders inside which particles are located. Received: 4 September 1997 / Revised: 14 October 1997 / Accepted: 19 November 1997     

Magneto-optical study of the orientation confinement of particles in ferrolyotropic systems

Ferrosmectics and ferrohexagonals are magnetic liquid crystals which consist of a lamellar and a hexagonal phase in which magnetic nanoparticles are incorporated. The magnetic field variation and the relaxation of the linear optical birefringence of ferrosmectics and ferrohexagonals and its time relaxation are measured in different geometries and compared with that of a ferrofluid sample. We interpret our data by the existence of a mean orientation of the magnetic particles in the lyotropic structure, which appears to be non-random in zero field. We conclude that the magnetic moments of the particles are preferentially aligned in the plane of the ferrosmectic layers and along the axis of the ferrohexagonal cylinders, respectively. To account for this preferred alignment, we propose that some of the particles in the ferrosmectic are adsorbed on the surfactant layers with their moment aligned in the lamellar plane, while the orientation of the moments in the ferrohexagonal is restricted to a cone around the cylinder axis. Received 31 December 1998 and Received in final form 22 September 1999     

Highly anisotropic elasticity of a dendrimeric liquid crystal

Magnetic and electrical Freedericksz measurements were performed on the second generation monodendritic liquid crystal G₂(OH). The deduced elastic constants were found to be exceptionally anisotropic: the splay elastic constant K₁₁ is more than an order of magnitude larger than the bend elastic constant K₃₃, and the twist constant K₂₂ is approximately twice K₃₃. The results are discussed in terms of molecular conformations. Received: 23 February 1998 / Revised and Accepted: 26 May 1998     

Polar nano-rods under shear: From equilibrium to chaos

The orientational dynamics of rod-like particles with permanent (electric or magnetic) dipole moments in a plane Couette shear flow is investigated using mesoscopic relaxation equations combined with a generalized Landau free energy. The free energy contribution due to the coupling between average alignment and dipole orientation is derived on a microscopic basis. Numerical results of the resulting eight-dimensional dynamical system are presented for the case of longitudinal dipoles and thermodynamic conditions where the equilibrium state is a (polar or non-polar) nematic. Solution diagrams reveal presence of a large variety of periodic, transient chaotic, and chaotic dynamic states of the average alignment and dipole moment, respectively, appearing as a function of Deborah number and tumbling parameter. Compared to rods without dipoles we observe a significant preference of out-of-plane kayaking-tumbling states and, generally, a higher sensitivity to the initial conditions including bistability. We also demonstrate that the average (electric) dipole moment characterizing most of the observed states yields electrodynamic (magnetic) fields of measurable strength.     

Azimuthal anchoring of nematic on undulated substrate: Elasticity memory

We measure the azimuthal anchoring energy of the nematic 5CB on sinusoidal holographic unidimensional and bidimensional gratings. We find that the anchoring strength is almost the same for all of the gratings and up to one order of magnitude stronger than expected by the topographic mechanism proposed by Berreman. We observe strong memory effects which dominate both the elastic anchoring and the easy axis gliding. We show that these memory effects limit from below the anchoring energy and are the main obstacle in the realization of substrates with weak anchoring conditions. Received: 29 April 1998 / Accepted: 23 June 1998     

Effect of surface electric field on the anchoring of nematic liquid crystals

We analyse the influence of adsorbed ions and the resulting surface electric field and its gradient on the anchoring properties of nematics with ionic conductivity. We take into account two physical mechanisms for the coupling of the nematic director with the surface electric field: (i) the dielectric anisotropy and (ii) the coupling of the quadrupolar component of the flexoelectric coefficient with the field gradient. It is shown that for sufficiently large fields near saturated coverage of the adsorbed ions, there can be a spontaneous curvature distortion in the cell even when the anchoring energy is infinitely strong. We also discuss the director distortion when the anchoring energy of the surface is finite. Received: 29 September 1997 / Received in final from: 10 November 1997 / Accepted: 18 November 1997     

Optical reflectivity study of synclinic and anticlinic structures in thin freely suspended smectic films

Optical reflectivity studies have been conducted on freely suspended films with synclinic and anticlinic structures. For the first time quantitative data were obtained on orientational ordering in films with anticlinic structure. In the same wide temperature range of more than 30 K we observed both transverse and longitudinal ferroelectricity in the films of the same thickness. Equilibrium transition temperatures between structures with transverse and longitudinal polarization were above the bulk transition temperature to the SmC phase. The molecule tilt was determined in superthin films with synclinic and anticlinic ordering. Received 29 October 1999 and Received in final form 17 February 2000     

Competition between ferroelectric and flexoelectric polarization in freely suspended smectic films

We report a detailed ellipsometric study of freely suspended films of chiral liquid-crystal compounds possessing smectic-A and smectic-C phases. In the temperature region between the smectic-A - smectic-C bulk and surface transitions, a discontinuous reconstruction of the tilt profile across the film is observed in the presence of a constant d.c. electric field. Comparison of the measured ellipsometric quantities with values calculated from model tilt profiles reveals a competition between a structure possessing a homogeneous tilt direction and large ferroelectric polarization and a structure with opposite tilt direction in the two film halfs and large flexoelectric polarization. Received 21 October 1998     

Thermally induced effects on the diffraction pattern of a dye doped nematic film

We investigate the effects produced on the diffraction pattern of a dyed nematic thin film under the action of an optical field and a low frequency AC electric field. For a homeotropically aligned mixture of the nematic E7 doped with a dichroic dye, a sequence of dynamical regimes of the far field diffraction pattern is observed. For specific values of the beam's power, frequency and amplitude of the AC field, a uniform steady rotational motion (SR) of the pattern sets in with a measured angular velocity ν_exp =2.58 Hz. To account for this and other observed features of the diffraction pattern an analytical model is proposed. This allows us to describe quantitatively the reorientation of the film, to calculate some specific structural features of the diffraction pattern, as well as its angular velocity. We find that the predicted angular velocity ν_theor=5.7 Hz, is in quite good agreement with the measured value.     

Helically modulated electroclinical effects in twist grain boundary liquid crystals

We report the first observation of an electroclinical effect at the TGB-TGB transition induced by an external DC electric field applied perpendicular to the pitch direction. Upon increasing the field, the smectic layers rather than the director field tilt over relative to the helical axis, allowing to detect the effect by X-ray scattering from well aligned samples. The observations are qualitatively interpreted in the frame of a mean field phenomenological model of a helically modulated electroclinical effect. Received: 24 April 1998 / Revised: 22 June 1998 / Accepted: 31 July 1998     

Orientational diffusivities measured by Rayleigh scattering in a lyotropic calamitic nematic () liquid crystal phase: the backflow problem revisited

Using a light-beating technique we have measured the damping time of thermal fluctuations of the nematic director for the so called cylindrical or calamitic nematic (N_C) phase of the lyotropic system K-laurate/decanol/. By varying the scattering angle in suitable geometries, we have been able to estimate the orientational diffusivities associated to the three pure deformations of splay, twist and bend. A former measurement made in the disk-like N_D phase of the same system yielded a large deviation between the splay and twist diffusivities. The effect was then attributed to induced flows, or backflow, which could be responsible for the reduction of the splay viscosity. In fact, this is the analogous effect, for disks, to the one recognized since long time ago arriving for rod-like molecules in a classical nematic, though in this case it is associated with bend deformations. The analogy comes about thanks to the interchange of the role played by disks and cylinders for, respectively, splay and bend fluctuations.The measurements reported here provide a new test on the applicability of the backflow model to a nematic system composed of micelles, that is, aggregates made of amphiphilic (surfactant) molecules, in its cylindrical-like variant, i.e. the N_C phase. In addition, the comparative study made here with the previous results existing in the literature for the N_D phase, allows us to conjecture on structural issues concerning lyotropic nematics. Received: 29 April 1998 / Revised: 19 August 1998 / Accepted: 31 August 1998     

Surface electric-field-induced instabilities in a homeotropically oriented nematic liquid crystal sample

The effect of a surface electric field produced by ionic adsorption on the molecular orientation of a nematic liquid crystal sample is analyzed. The eigenvalue problem for a semi-infinite medium is analytically solved both for strong and weak anchoring situations. The threshold instabilities are numerically determined and it is shown that the homeotropic pattern can be destabilized also in the situation of strong anchoring. The dependence of the threshold field on the anchoring strength and on the surface polarization is determined by taking into account also the coupling of the quadrupolar component of the flexoelectric coefficient with the field gradient. Received 4 November 1999 and Received in final form 4 April 2000     

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     

Effect of a strong electric field on a nematogen: evidence for polar short range order

We present experimental studies on the effect of strong electric fields on the nematogen p-cyanophenyl p-n-heptyl benzoate which has the strongly polar cyano end group and a large positive dielectric anisotropy. We use a local temperature measurement to take into account heating effects and an electrical impedance analysis to determine both the dielectric constant () and the resistance (R) of the sample. We also measure the higher harmonic responses of the medium. The new results obtained in this study are: (i) a detailed temperature dependence of the terms which describe (a) the quenching of macroscopic thermal fluctuations of the nematic director and (b) the enhancement of the orientational order parameter due to Kerr effect, (ii) clear evidence for the critical divergence of susceptibility as reflected in the third harmonic signal, (iii) an unusual enhancement of the conductivity which shows a large peak just below the critical point , (iv) a significant peak in the second harmonic signal at and (v) evidence for a field induced nematic-nematic transition well inside the nematic range. We argue that the results (iii)-(v) indicate the presence of polar short range order in the medium and hence support a molecular model in which such an order has been proposed. Received: 15 July 1997 / Received in final form: 24 September 1997 / Accepted: 29 October 1997     

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     

New problems of particle transfer in ferrocolloids: Magnetic Soret effect and thermoosmosis

The paper deals with critical reviewing of the experiments on thermodiffusion in ferrocolloids. The observed magnetic Soret effect is much stronger than that predicted theoretically. It is shown that the main reason of that is the influence of the magnetic field on mass diffusion. Besides, some measurements are affected by uncontrolled thermal and solutal magnetic convection. In porous media, when macroscopic convection is suppressed, thermodiffusion is accompanied by thermoosmosis as well as by a microconvective mass transfer induced by particle magnetophoresis on filter grains.     

Different mechanisms of nucleation and self-organization of droplets in ferroelectric smectic membranes

New mechanisms of droplet nucleation and self-organization in ferroelectric membranes are described. The droplets may be accompanied by different number of topological defects (zero, one, two) whose location may be on the droplet boundary or in the membrane. Nucleation and self-organization of droplets with total topological charge S = 0 , S = + 1 and S = - 1 were investigated. We found that an S = - 1 topological defect may be the center of both droplet nucleation and chain formation. This mechanism of chaining drastically differs from the droplet self-organization described earlier which is realized by attraction of droplet-defect pairs. Our observations demonstrate new possibilities for manipulating the inclusions and their self-organization in smectic membranes.     

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     

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.