Jan P. F. Lagerwall

Carbon nanotubes in liquid crystals

We review the research on carbon nanotube (CNT) dispersion in liquid crystals (LCs), focusing mainly on the approaches where the aim is to align CNTs along the LC director field, but also covering briefly the proposed possibility to enhance thermotropic LCs by CNT doping. All relevant LC types are considered: thermotropic LC hosts allowing dynamic CNT realignment, lyotropic LC hosts allowing very high concentration of CNTs uniformly aligned over macroscopic areas and consequent removal of the LC, and LC phases formed by CNTs themselves, used in spinning high-quality carbon nanotube fibres. We also discuss the issue of CNT dispersion in some detail, since successful nanotube separation is imperative for success in this field regardless of the type of LC that is considered. We end by defining a few major challenges for the development of the field over the next few years, critical for reaching the stage where industrially viable protocols for LC-based CNT alignment can be defined.

Antiferroelectric liquid crystals with 45° tilt - a new class of promising electro-optic materials

Abstract Antiferroelectric liquid crystals with a tilt angle of 45 degrees have very interesting optical properties, which seem to have been overlooked so far - perhaps because such materials have hardly been available. We have prepared a four-component mixture of partially fluorinated compounds with a SmCa* phase in the interval between 27.4°C and 121.6°C, in which the tilt angle θ saturates at 45 degrees for T≤80°C, and we investigate the optical properties, theoretically and experimentally. One of the surprising features of 45 degree materials is that they permit a remarkably high contrast by virtue of an excellent dark-state, in spite of the fact that AFLC materials are notoriously difficult to align. This is because a 45° AFLC turns out to be (negatively) uniaxial instead of biaxial. We describe these properties and propose a number of potentially interesting new applications, including a polarizer-free display mode and a three-level “phase-only” modulator.

One-piece micropumps from liquid crystalline core-shell particles

Responsive polymers are low-cost, light weight and flexible, and thus an attractive class of materials for the integration into micromechanical and lab-on-chip systems. Triggered by external stimuli, liquid crystalline elastomers are able to perform mechanical motion and can be utilized as microactuators. Here we present the fabrication of one-piece micropumps from liquid crystalline core-shell elastomer particles via a microfluidic double-emulsion process, the continuous nature of which enables a low-cost and rapid production. The liquid crystalline elastomer shell contains a liquid core, which is reversibly pumped into and out of the particle by actuation of the liquid crystalline shell in a jellyfish-like motion. The liquid crystalline elastomer shells have the potential to be integrated into a microfluidic system as micropumps that do not require additional components, except passive channel connectors and a trigger for actuation. This renders elaborate and high-cost micromachining techniques, which are otherwise required for obtaining microstructures with pump function, unnecessary.

Coaxial electrospinning of microfibres with liquid crystal in the core

Liquid crystal containing composite fibres were produced via coaxial electrospinning, demonstrating that this technique can be used for producing new functional fibres and/or to study the impact of extreme confinement on liquid crystal phases.

Macroscopic Control of Helix Orientation in Films Dried from Cholesteric Liquid-Crystalline Cellulose Nanocrystal Suspensions

The intrinsic ability of cellulose nanocrystals (CNCs) to self-organize into films and bulk materials with helical order in a cholesteric liquid crystal is scientifically intriguing and potentially important for the production of renewable multifunctional materials with attractive optical properties. A major obstacle, however, has been the lack of control of helix direction, which results in a defect-rich, mosaic-like domain structure. Herein, a method for guiding the helix during film formation is introduced, which yields dramatically improved uniformity, as confirmed by using polarizing optical and scanning electron microscopy. By raising the CNC concentration in the initial suspension to the fully liquid crystalline range, a vertical helix orientation is promoted, as directed by the macroscopic phase boundaries. Further control of the helix orientation is achieved by subjecting the suspension to a circular shear flow during drying.

Tuneable multicoloured patterns from photonic cross-communication between cholesteric liquid crystal droplets

Monodisperse droplets of planar-aligned cholesteric (N*) liquid crystal exhibit an intriguing capacity for photonic cross-communication, giving rise to colourful patterns that depend sensitively on the N* pitch, droplet positions and illuminated area. The phenomenon results from a combination of omnidirectional selective reflection of N* droplets—which thus act as spherically symmetric self-assembled photonic crystals—and total internal reflection at the continuous phase surface. We outline how the unique optical properties can be employed in numerous applications.

The case of thresholdless antiferroelectricity: polarization-stabilized twisted SmC* liquid crystals give V-shaped electro-optic response

We have studied the three-component liquid crystal mixture reported to exhibit ‘thresholdless antiferroelectricity’ [Inui et al., J. Mater. Chem., 1996, 6, 671]. We find that the thresholdless or V-shaped switching is obtained in the absence of antiferroelectricity. This analog electro-optic response is due to the field-induced switching of a twisted smectic C* structure stabilized by polar surface interactions and by electrostatic bulk polarization charge interactions. The latter confine the director twist to thin surface regions leaving the bulk of the cell uniform, which gives good extinction at zero field. In sufficiently thin cells, such thresholdless switching can in fact be followed down to much lower temperatures, where the bulk would be antiferroelectric, but is maintained in the cells in the ferroelectric state by hysteresis from surface action.

Rod Packing in Chiral Nematic Cellulose Nanocrystal Dispersions Studied by Small-Angle X-ray Scattering and Laser Diffraction

The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small-angle X-ray scattering (SAXS) and laser diffraction. The average separation distance between the CNCs and the average pitch of the chiral nematic phase have been determined over the entire isotropic-anisotropic biphasic region. The average separation distances range from 51 nm, at the onset of the anisotropic phase formation, to 25 nm above 6 vol % (fully liquid crystalline phase) whereas the average pitch varies from ≈15 μm down to ≈2 μm as ϕ increases from 2.5 up to 6.5 vol %. Using the cholesteric order, we determine that the twist angle between neighboring CNCs increases from about 1° up to 4° as ϕ increases from 2.5 up to 6.5 vol %. The dependence of the twisting on the volume fraction was related to the increase in the magnitude of the repulsive interactions between the charged rods as the average separation distance decreases.

Ferroelectric polysiloxane liquid crystals with ‘de Vries’-type smectic A*–smectic C* transitions

We report preliminary results of optical and small angle X-ray scattering (SAXS) experiments on the smectic A*−smectic C* transition in two ferroelectric liquid crystalline polysiloxanes. Although the optical tilt angle in the SmC* phases reaches values up to 30°, temperature-dependent SAXS measurements clearly reveal that the smectic layer spacing is basically conserved during the A*–C* transition as well as in the subsequent C* phase. Connected with the A*–C* transition we further observed a significant increase in birefringence, hence reflecting an increase of orientational order. The practical absence of layer shrinkage and the enhanced orientational ordering are consistent with the de Vries diffuse cone model of smectic A−smectic C transitions.

On the phase sequence of antiferroelectric liquid crystals and its relation to orientational and translational order

The substance MHPOBC is the oldest and still most important reference antiferroelectric liquid crystal (AFLC). There is still considerable controversy concerning the correct phase designations for this material and, in particular, about the presence or absence of SmC* in its phase sequence. By means of dielectric spectroscopy and polarizing microscopy, we show that whereas the pure compound lacks the SmC* phase, this phase rapidly replaces the SmC*β subphase through the reduced purity resulting from temperature-induced chemical degradation which is hard to avoid under standard experimental conditions. X-ray investigations furthermore show that this change in phase sequence is coupled to a decrease in translational order. This explains the large variations in the reported phase sequence and electro-optic behaviour of MHPOBC, in particular concerning the SmC*β phase which has been said to exhibit ferro-, ferri- as well as antiferroelectric properties. It is likely that the sensitivity of the AFLC phase sequence to sample purity is a general property of AFLC materials. We discuss the importance of optical and chemical purity as well as tilt and spontaneous polarization for the observed phase sequence and propose that one of the key features determining the existence of the different tilted structures is the antagonism between orientational (nematic) and translational (smectic) order. The decreased smectic order (increased layer interdigitation) imposed by chemical impurities promotes the synclinic SmC* phase at the cost of the AFLC phases SmC*α, SmC*β, SmC*γ and SmC*a. We also propose that the SmA* phase in FLC and AFLC materials may actually have a somewhat different character and, depending on its microstructure, some of the tilted phases can be expected to appear or not to appear in the phase sequence. AFLC materials exhibiting a direct SmA* -SmC*a transition are found to be typical ‘de Vries smectics’, with very high orientational disorder in the SmA* phase. Finally, we discuss the fact that SmC*β and SmC*γ have two superposed helical superstructures and explain the observation that the handedness of the large scale helix may very well change sign, while the handedness on the unit cell level is preserved.