Orientational order induced by a polymer network in the isotropic phase of liquid crystal.

We studied the paranematic ordering induced by a polymer network in the isotropic phase of a liquid crystal (LC) that occurs in polymer-stabilized cells with bend configuration of the LC director (π cells) fabricated via photopolymerization of photoreactive monomer RM 82 added in small concentrations (3-5 wt %) to a nematic LC [4-cyano-4'-pentylbiphenyl (5CB)] when low voltage was applied across the cell. The polymer network formed in the nematic phase of the LC consists of fine fibrils that are aligned along the LC director and thus mirror the bend deformation of the LC at the time of polymerization. When heated to temperatures above the nematic-to-isotropic (N-I) phase transition such highly ordered polymer network anchors LC molecules providing ordering of the LC around the fibrils which results in unusually high optical retardation of the cell, R_{cell}. We present a theoretical model that relates R_{cell} to the degree of order of the fibrils, the anchoring energy of the LC molecules on the surface of the polymer fibrils, and the fibril radius r_{0}. Fitting of the experimental R_{cell}(T) curves with the developed model reveals correlation of r_{0} with the nematic correlation length ξ_{0} which characterizes penetration of the nematic order in the isotropic phase of the LC. Accepting ξ_{0} as a material constant of about 1 nm leads to a very small radius of the fibrils, r_{0}∼1nm, which is also supported by other reported experimental data. High optical retardation and fast electro-optical response of the cells at the temperatures deep into the isotropic phase point toward the enhancement of the polymer-induced paranematic order by a well-oriented layer of LC molecules that are absorbed on the surface of fibrils. Application of high voltage at the isotropic phase temperatures results in high variations of the optical retardation of the cells. Characteristic on and off response times were about 10-100 µs, independent of the cell gap. Combination of large voltage-driven changes of the optical retardation occurring in the low-viscosity isotropic state with switching times that are at least two orders of magnitude shorter than the typical relaxation times of the cells operating in the nematic phase make such polymer-stabilized π cells very promising for application in fast electro-optical switches and light modulators.

Comparative study of the anchoring strength of reactive mesogens and industrial polyimides used for the alignment of liquid crystals.

We measured the Rapini-Papoular polar anchoring strength coefficient W for 4^{'}-pentyl-4-cyanobiphenyl (5CB) on alignment layers formed by the reactive mesogen photopolymers RM 257, RM 82, and RM 84 [4,4^{'}-bis(acryloyl)biphenyl] (by Merck). These materials are commonly used for the photostabilization of the liquid crystal (LC) director in the bulk as well as at the surface of the LC layer via the formation of a loose polymer network that captures the director orientation. We developed a method of fabrication of alignment layers from these polymers, and estimated W from the measurements of the optical retardation as a function of applied voltage in uniformly aligned cells. We found that RM 257 yielded W of about 6×10^{-4}J/m^{2}, whereas RM 82 and RM 84 provided anchoring strengths of about 2×10^{-4} and 4×10^{-4}J/m^{2}, respectively. Subsequent heating of the sample either destroyed the alignment layer, or substantially decreased W to about 1×10^{-4}J/m^{2}, which was comparable to the anchoring strength of weakly rubbed commercial polyimides.

DH(*) in chiral smectics under electric field.

The behavior of double helices (DH(*) formed in the temperature interval N(*) -SmA(*) in compounds of non-chiral liquid crystals doped with chiral molecules was investigated. Two different systems presenting left-handed and right-handed chirality were studied. A statistics of the handedness of the DH(*) revealed a correlation with the mixture chirality, as predicted theoretically in C. Meyer, Yu. A. Nastishin, M. Kleman, Phys. Rev. E 82, 031704 (2010). By applying a gradually increasing AC electric field, one can observe the shrinking of the cylinder circumscribing the DH(*) . This shrink is accompanied by a reduction of the DH(*) 's pitch. This effect was similar to the one produced by the decrease of temperature in the absence of the field.

Local distortion energy and coarse-grained elasticity of the twist-bend nematic phase.

The recently discovered twist-bend nematic phase of achiral bent-shaped molecules, NTB, has a doubly degenerate ground-state with a periodically modulated heliconical structure and unusual distortion elasticity, the theoretical description of which is still debated. We show that the NTB phase has the same macroscopic symmetry as another periodic mesophase, the chiral smectic-A, SmA*. Based on this NTB/SmA* analogy, we develop a coarse-grained elastic model for the NTB phase. Adopting one of the existing microscopic NTB elastic models, we calculate the coarse-grained elastic constants, coherence and penetration lengths in terms of a few Frank-like nematic elastic coefficients that can be measured in macroscopic experiments. The same coarse-grained approach, applied to different local elastic models, may provide an efficient experimental test of their validity. We show that the anisotropy of the NTB coarse-grained elasticity is opposite to that of the SmA*, leading probably to different configurations of some of the defects of the "layered" NTB structure. Moreover, we argue that the intrinsic chiral frustration of the NTB phase may be resolved by penetration of the twist field into the bulk through a network of screw dislocations of the NTB pseudo-layers, resulting in a twist-bend analogue of the twist grain boundary phase TGBA.

Flexoelectrically driven electroclinic effect in the twist-bend nematic phase of achiral molecules with bent shapes.

We extend the twist-bend nematic (N(TB)) model to describe the electro-optics of this novel phase. We predict an electroclinic effect (ECE) subject to a dc electric field E applied perpendicular to the helix axis or wave vector q, with rotation of the N(TB) optic axis around E. This linear effect, with its flexoelectric origin, is a close analog to the electro-optic effects observed for chiral liquid crystals. However, in nematics composed of achiral molecules having a bent shape, it is the electro-optic signature of the N(TB) phase. We test our model experimentally in the low-temperature nematic phase of the odd liquid crystal dimer, CB7CB, with its molecules having, on average, a bent shape. The ECE measurements confirm the previously proposed twist-bend nematic structure of this phase, with its broken chiral symmetry, extremely short (<10 nm) doubly degenerate pitch and ultrafast, submicrosecond response times.

Electric-field-induced perfect anti-nematic order in isotropic aqueous suspensions of a natural beidellite clay.

We study the electric-field-induced birefringence and orientational order in the isotropic phase of aqueous suspensions of exfoliated natural beidellite clay particles, thin (L = 0.65 nm) flat charged sheets with high aspect ratio, D/L ≈ 300. Our electric birefringence experiment is optimized for aqueous suspensions of colloidal particles, with a high frequency a.c. electric field, ν ≈ 1 MHz, applied by two external electrodes to a thin flat sample, sealed in an optical capillary. In isotropic and biphasic samples, we observed strong field-induced birefringence Δn(E), saturating at moderate E(sat) field to a plateau Δn(sat) proportional to the volume fraction ϕ. The field-induced order parameter S(E) is negative and saturates to S(sat) = -0.5 above E(sat). This corresponds to a perfect "anti-nematic" order, i.e. the normals of the beidellite particles are perpendicular to the field, without any preferred azimuthal direction. The measured specific excess polarizability ΔA(sp) is among the highest data reported for other strongly anisometric dielectric and metal particles. We explain the high ΔA(sp) value with the strong induced polarization of the electric double layer of counterions at the charged particle/electrolyte interface. The estimated equivalent conductivity of the beidellite particle K(eq) = 2 K(σ)/L is several orders of magnitude larger than the bulk conductivity of the electrolyte K(e), resulting in a metal-like behavior of the beidellite disks under field. In the isotropic regions of biphasic nematic/isotropic samples, the excess polarizability is further enhanced by an order of magnitude, indicating collective reorientation of the particles. We propose that this enhancement might be due to pretransitional fluctuations of the spontaneous nematic order S(N) of the colloidal suspension and/or formation of chains of particles, with antinematic order of the beidellite disks in the chains.

Magnetic-field-induced nematic-nematic phase separation and droplet formation in colloidal goethite.

We demonstrate the suitability of polarization microscopy to study the recently discovered (parallel) nematic-(perpendicular) nematic phase separation. This novel type of phase transition is induced by applying an external magnetic field to a nematic liquid crystal of boardlike colloidal goethite and is due to an interplay between the intrinsic magnetic properties of goethite and the collective effect of liquid crystal formation. It is shown that the intense ochre colour of goethite does not preclude the use of polarization microscopy and interference colours, and that dichroism can give valuable qualitative information on the nature of the phases, their anchoring and their sedimentation and order parameter profiles. We also apply these techniques to study 'nematic-nematic tactoids': nematic droplets sedimenting within a nematic medium with mutually perpendicular orientations.

Liquid-crystalline nematic phase in aqueous suspensions of a disk-shaped natural beidellite clay.

After size-selection and osmotic pressure measurements at fixed ionic strength, the behavior of aqueous colloidal suspensions of anisotropic disklike beidellite clay particles has been investigated by combining optical observations under polarized light, rheological, and small angle X-ray scattering (SAXS) experiments. The obtained phase diagrams (volume fraction/ionic strength) reveal, for ionic strength below 10(-3) M/L, a first-order isotropic/nematic (I/N) phase transition before gel formation at low volume fractions, typically around 0.5%. This I/N transition line displays a positive slope for increasing ionic strength and shifts toward lower volume fraction with increasing particle size, confirming that the system is controlled by repulsive interactions. The swelling laws, derived from the interparticle distances obtained by SAXS, display a transition from isotropic swelling at low volume fractions to lamellar swelling at higher volume fractions. The liquid-crystal properties have then been investigated in detail. Highly aligned nematic samples can be obtained in three different ways, by applying a magnetic field, an ac electric field, and by spontaneous homeotropic anchoring on surfaces. The birefringence of the fluid nematic phase is negative with typical values around 5 x 10(-4) at a volume fraction of about 0.6%. High nematic order parameters have been obtained as expected for well-aligned samples. The nematic director is aligned parallel to the magnetic field and perpendicular to the electric field.

Anticonical anchoring and surface transitions in a nematic liquid crystal.

Recent works reported planar and conical azimuthally degenerated nematic anchorings. Here we predict an additional "anticonical" degenerated anchoring. Its energy presents two minima, parallel and perpendicular to the substrate plane, separated by a conical energy barrier. We realize this bistable anchoring on a grafted polymer brush and we observe temperature-driven transitions between the conical, planar, and anticonical degenerated anchorings. Under electric field we break the anticonical anchoring and switch between its bistable states.

Physical properties of aqueous suspensions of goethite (alpha-FeOOH) nanorods. Part I: In the isotropic phase.

Depending on volume fraction, aqueous suspensions of goethite (alpha-FeOOH) nanorods form a liquid-crystalline nematic phase (above 8.5%) or an isotropic liquid phase (below 5.5%). In this article, we investigate by small-angle X-ray scattering, magneto-optics, and magnetometry the influence of a magnetic field on the isotropic phase. After a brief description of the synthesis and characterisation of the goethite nanorod suspensions, we show that the disordered phase becomes very anisotropic under a magnetic field that aligns the particles. Moreover, we observe that the nanorods align parallel to a small field (< 350 mT), but realign perpendicular to a large enough field (> 350 mT). This phenomenon is interpreted as due to the competition between the influence of the nanorod permanent magnetic moment and a negative anisotropy of magnetic susceptibility. Our interpretation is supported by the behaviour of the suspensions in an alternating magnetic field. Finally, we propose a model that explains all experimental observations in a consistent way.

Physical properties of aqueous suspensions of goethite (alpha-FeOOH) nanorods. Part II: In the nematic phase.

At volume fractions larger than 8.5%, aqueous suspensions of lath-like goethite (alpha-FeOOH) nanorods form a lyotropic nematic phase. In this article, we first discuss the nematic ordering within statistical-physics models of the isotropic/nematic phase transition. We then describe the influence of a magnetic field on the nematic phase. Because the nanorods bear permanent magnetic moments, the nematic suspensions have dipolar order and very low Frederiks thresholds. Moreover, the nematic phase aligns parallel to a small magnetic field but realigns perpendicular to a high field because of a competition between the permanent moments of the nanorods and their negative anisotropy of magnetic susceptibility. This magneto-optical study of the nematic phase is completely consistent with that of the isotropic phase of the same suspensions published in Part I (this issue, p. 291). Besides, we demonstrate the field-induced biaxiality of a nematic single domain aligned perpendicular to the field. We also describe here preliminary experiments where an a.c. electric field is applied to the nematic phase. Both field amplitude and frequency were found to control the alignment direction and homeotropic-to-planar alignment transitions were observed. From this data, simple models were used to estimate some physical constants of the nematic phase.

Biaxial melting of the nematic order under a strong electric field.

We study the action of a strong electric field on a nematic, topologically stabilized with director n perpendicular to E. Above a threshold field the nematic order on the cell midplane is "melted" and rapidly reconstructed with n axially E. In a Landau-de Gennes model, we show that the observed transient "melted" state is a biaxial nematic and not an isotropic liquid.

Anchoring screening of defects interaction in a nematic liquid crystal.

The relaxation dynamic of a dipole of +1/2 and -1/2 parallel disclination lines in a confined geometry is measured. The confinement and the planar anchoring conditions force the disclinations to be normal to the glass plates. In a first asymptotic regime, the direct elastic interaction between disclination is completely screened out by the anchoring energy. In a second regime, corresponding to the final annihilation steps, the dynamic follows the square-root law predicted by de Gennes for two isolated and parallel disclinations. The annihilation dynamic, in the asymptotic regime, is in good agreement with an elastic model based on an electrostatic analogy.

Outstanding magnetic properties of nematic suspensions of goethite (alpha-FeOOH) nanorods.

Aqueous suspensions of goethite (alpha-FeOOH) nanorods form a mineral lyotropic nematic phase that aligns in a very low magnetic field (20 mT for samples 20 microm thick). The particles orient along the field direction at intensities smaller than 350 mT, but they reorient perpendicular to the field beyond 350 mT. This outstanding behavior is also observed in the isotropic phase which has a very strong magnetic-field induced birefringence that could be interesting for applications. We interpret these magnetic effects as resulting from a competition between a nanorod remanent magnetic moment and a negative anisotropy of its magnetic susceptibility.

Memory-free conic anchoring of liquid crystals on a solid substrate

We show that the anchoring memory of liquid crystals on solid substrates can be completely removed by grafting highly mobile polymer chains. Using grafted polystyrene, we obtain uniform, stable, and reproducible memory-free and conically degenerated anchoring of the nematic 5CB. The symmetry of the conic anchoring enables two different zenithal anchoring breakings, towards homeotropic and planar states. Under external torques we observe both of them, with weak thresholds.