Samuel Sprunt

Twist-bend nematic liquid crystals in high magnetic fields.

We present magneto-optic measurements on two materials that form the recently discovered twist-bend nematic (N_{tb}) phase. This intriguing state of matter represents a fluid phase that is orientationally anisotropic in three directions and also exhibits translational order with periodicity several times larger than the molecular size. N_{tb} materials may also spontaneously form a visible, macroscopic stripe texture. We show that the optical stripe texture can be persistently inhibited by a magnetic field, and a 25T external magnetic field depresses the N-N_{tb} phase transition temperature by almost 1{∘}C. We propose a quantitative mechanism to account for this shift and suggest a Helfrich-Hurault-type mechanism for the optical stripe formation.

Short-Range Smectic Order in Bent-Core Nematic Liquid Crystals

Small angle X-ray diffraction from the uniaxial nematic phase of certain bent-core liquid crystals is shown to be consistent with the presence of molecular clusters possessing short-range tilted smectic (smectic-C) order. Persistence of these clusters throughout the nematic phase, and even into the isotropic state, likely accounts for the unusual macroscopic behavior previously reported in bent-core nematics, including an anomalously large flexoelectric effect (∼ 1000 times that of conventional calamitic nematics), very large orientational and flow viscosities (∼ 10–100 and ∼ 100–1000 times, respectively, typical values for calamitics), and an extraordinary flow birefringence observed in the isotropic state.

Giant flexoelectricity in bent-core nematic liquid crystal elastomers

Recently ferroelectric ceramic and bent-core nematic liquid crystals have demonstrated flexoelectricity (coupling between curvature strains to electric polarization) up to 104 times larger than the previous standards. This may allow for usable electromechanical devices. However, ceramics are too rigid to withstand large bending and bent-core nematic fluids must be physically supported—their technological applicability is still limited. In this paper, we show that novel side-chain bent-core nematic elastomers not only produce giant flexoelectricity but are also robust and flexible enough for microscale parasitic power generation.

Viscosities of a bent-core nematic liquid crystal

Viscosity measurements are reported for a bent‐core nematic liquid crystal, 4‐ chloro‐1,3‐phenylenebis{4‐[4′‐(9‐decenyloxy)benzoyloxy]} benzoate (ClPbis10BB). The rotational viscosity was measured by analysing the dynamics of director rotation in pulsed magnetic fields, and the flow viscosities were determined by employing a new electro‐rotation technique. The results show that whereas the rotational viscosity is more than ten times larger than for calamitic liquid crystals, the flow viscosity is more than 100 times larger. Even more striking is the difference between the ratio of the flow and rotational viscosities, which for calamitic nematics is typically 0.1, whereas in this bent‐core material it is ∼50. This suggests that the large shear viscosity is primarily due not so much to the molecular size, but rather the shape. A model is discussed that may explain the observations.

Search for biaxiality in a shape-persistent bent-core nematic liquid crystal

Using a range of optical techniques, we have probed the nature of orientational order in a thermotropic bent-core liquid crystal, which features a shape-persistent molecular architecture designed to promote a biaxial nematic phase. In the upper range of the nematic phase (enantiotropic regime), dynamic light scattering reveals strong fluctuations attributable to the biaxial order parameter, in addition to the usual uniaxial director modes. Assuming a Landau-type expansion of the orientational free energy, we estimate the correlation length associated with these fluctuations to be ∼100 nm. At lower temperatures, and mainly in the monotropic regime of the nematic, we observe by optical conoscopy an apparently biaxial texture, which develops when the sample temperature is changed but then relaxes back to a uniaxial state over time scales much longer than observed in the light scattering measurements. A combination of fluorescence confocal polarizing microscopy and coherent anti-Stokes Raman scattering confirms that the conoscopic texture arises from a flow-induced reorientation of the molecules, associated with a large thermal expansion coefficient of the material, rather than from the spontaneous development of a macroscopic secondary optical axis. We discuss a model to account for the observed behavior at both high and low temperatures based on the temperature-dependent formation of nanoscale, biaxially ordered complexes among the bent-core molecules within a macroscopically uniaxial phase.

Rheological properties of bent-core liquid crystals

We show that bent-core liquid crystalline materials exhibit non-Newtonian flow in their optically isotropic liquid phase. We conjecture that this behavior is due to the existence of nanostructured, fluctuating clusters composed of a few smectic-like layers. Shear alignment of these clusters explains the shear thinning observed in bent-core liquid crystals having either a nematic phase or non-modulated smectic phase. By contrast, smectogens having a modulated smectic phase do not shear thin at low shear rates, but even show a slight shear thickening which may be due to entanglements of wormlike and/or helical clusters.

Self-assembly, condensation, and order in aqueous lyotropic chromonic liquid crystals crowded with additives†

Dense multicomponent systems with macromolecules and small solutes attract a broad research interest as they mimic the molecularly crowded cellular interiors. The additives can condense and align the macromolecules, but they do not change the degree of covalent polymerization. We chose a lyotropic chromonic liquid crystal with reversibly and non-covalently assembled aggregates as a much softer system, reminiscent of “living polymers”, to demonstrate that small neutral and charged additives cause condensation of aggregates with ensuing orientational and positional ordering and nontrivial morphologies of phase separation, such as tactoids and toroids of the nematic and hexagonal columnar phase coexisting with the isotropic melt. Scanning transmission X-ray microscopy (STXM) with near edge X-ray absorption fine structure (NEXAFS) analysis as well as fluorescent microscopy demonstrates segregation of the components. The observations suggest that self-assembly of chromonic aggregates in the presence of additives is controlled by both entropy effects and by specific molecular interactions and provide a new route to the regulated reversible assembly of soft materials formed by low-molecular weight components.

POLYMER-STABILIZED DIFFRACTION GRATINGS FROM CHOLESTERIC LIQUID CRYSTALS

We report the use of a low concentration polymer network to stabilize electric field-induced diffraction gratings in cholesteric liquid crystals. The stabilized gratings can be electrically switched between a zero-field “on” state, which exhibits approximately 75% diffraction efficiency, and a moderate field (typically 3 V/μm) “off” state. Grating spacings between 1.7 and 30 μm are obtained in a 10 μm thick cell by variation of the concentration of chiral dopant used to form the cholesteric liquid crystal.

Flow properties of a twist-bend nematic liquid crystal

We present the first shear alignment studies and rheological measurements in the twist-bend nematic (Ntb) liquid crystal phase of odd numbered flexible dimer molecules. It is found that the Ntb phase is strongly shear-thinning. At shear stresses below 1 Pa the apparent viscosity of Ntb is 1000 times larger than in the nematic phase. At stress above 10 Pa the Ntb viscosity drops by two orders of magnitude and the material exhibits Newtonian fluid behavior. This is consistent with the heliconic axis becoming normal to the shear plane via shear-induced alignment. From measurements of the dynamic modulus we estimate the compression modulus of the pseudo-layers to be B ∼ 2 kPa; this value is discussed within the context of a simple theoretical model based upon a coarse-grained elastic free energy.

Morphology-dependent switching of polymer-stabilized cholesteric gratings

The use of a fingerprint texture of a cholesteric liquid crystal is demonstrated as a template to direct the formation of periodically ordered micro-size polymer walls. The morphology-property correlation of polymer-stabilized cholesteric gratings (PSCGs) was established for mesogenic and non-mesogenic reactive monomers. These PSCGs are suitable for laser beam steering, control of fibre optic signal and dynamic focus lenses.