Combining responsiveness and durability in liquid crystal-functionalised electrospun fibres with crosslinked sheath

in Liquid Crystals (2021)

Responsive functional composite fibre mats that are mechanically stable and impervious to water exposure are produced by coaxial electrospinning of thermotropic liquid crystal (LC) core inside a water ... [more ▼]

Responsive functional composite fibre mats that are mechanically stable and impervious to water exposure are produced by coaxial electrospinning of thermotropic liquid crystal (LC) core inside a water-based solution of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) forming the sheath. Because thermotropic LCs usually cannot be spun inside water-based solutions due to excessive interfacial tension γ, a n enabling step is the addition of ethanol or dioxane to the LC as a co-solvent compatible with both core and sheath fluids. This reduces γ sufficiently that coaxial jet spinning is possible. After spinning, thermal cross-linking of the PVA+PAA sheath yields LC-functionalised fibres that can be manipulated by hand and remain intact even upon full immersion in water. The LC core retains its behaviour, nematics showing well-aligned birefringence and transitioning to isotropic upon heating above the clearing point, and cholesterics showing selective reflection which is even enhanced upon water immersion due to the removal of sheath scattering. Our results pave the way to producing LC-functionalised responsive fibre mats using durable polymer sheaths, thereby enabling numerous innovative applications in wearable technology, and they also open new opportunities to study LCs in confinement, without visible impact of the container walls. [less ▲]

Influence of head group and chain length of surfactants used for stabilising liquid crystal shells

in Liquid Crystals (2018), 45(13-15), 2319-2328

We investigate the stability and textural development in nematic liquid crystal (LC) shells, with aqueous interior and exterior, as a function of the type and concentration of surfactant stabiliser of the ... [more ▼]

We investigate the stability and textural development in nematic liquid crystal (LC) shells, with aqueous interior and exterior, as a function of the type and concentration of surfactant stabiliser of the shell interfaces. The LC is the common thermotropic nematic 5CB and the surfactants are commercial, of cat- as well as of anionic type, with varying alkyl chain length. In addition to stabilising the shell interfaces, surfactants are generally assumed to promote radial (homeotropic) LC alignment, based on prior studies where the surfactant concentration was well above the critical micelle concentration (CMC). Here, we focus on the low-concentration range, below CMC. We find that both cat- and anionic surfactants can stabilise shells, although the higher water solubility of cationics can render stabilisation more difficult. We also conclude that surfactants do not necessarily impose homeotropic alignment; if the surfactant concentration is very low, the director may adopt planar alignment at the 5CB–water interface. Interestingly, the threshold concentration, where the surfactant takes control of alignment, is different for the shell inside and outside. Shells stabilised by solutions of surfactant with concentration near the threshold may therefore adopt a hybrid configuration, with homeotropic inside and planar outside. [less ▲]

Non-electronic gas sensors from electrospun mats of liquid crystal core fibers for detecting volatile organic compounds at room temperature

in Liquid Crystals (2016)

Non-woven mats comprised of liquid crystal-functionalised fibres are coaxially electrospun to create soft gas sensors that function non-electronically, thus requiring no power supply, detect- ing organic ... [more ▼]

Non-woven mats comprised of liquid crystal-functionalised fibres are coaxially electrospun to create soft gas sensors that function non-electronically, thus requiring no power supply, detect- ing organic vapours at room temperature. The fibres consist of a poly(vinylpyrrolidone) (PVP) sheath surrounding a core of nematic 4-cyano-4ʹpentylbiphenyl (5CB) liquid crystal. Several types of mats, containing uniformly cylindrical or irregular beaded fibres, in uniform or random orientations, are exposed to toluene vapour as a representative volatile organic compound. Between crossed polarisers all mats respond with a fast (response time on the order of a second or faster) reduction in brightness during gas exposure, and they return to the original state upon removal of the gas almost as quickly. With beaded fibres, the response of the mats is visible even without polarisers. We discuss how variations in fibre spinning conditions such as humidity level and the ratio of core-sheath fluid flow rates can be used to tune fibre morphology and thereby the response. Considering future development perspectives, we argue that fibres turned respon- sive through the incorporation of a liquid crystal core show promise as a new generation of sensors with textile form factor, ideal for wearable technology applications. [less ▲]

The peculiar optic, dielectric and x-ray diffraction properties of a fluorinated de vries asymmetric-diffuse-cone-model ferroelectric liquid crystal

in Liquid Crystals (2006), 33(1), 17-24

A new semi-fluorinated chiral smectic liquid crystal, W504, is investigated by electro-optic, dielectric and X-ray scattering experiments. It exhibits a huge dielectric soft mode response, strong ... [more ▼]

A new semi-fluorinated chiral smectic liquid crystal, W504, is investigated by electro-optic, dielectric and X-ray scattering experiments. It exhibits a huge dielectric soft mode response, strong electroclinic effect and a birefringence which increases considerably with the director tilt angle theta; typical characteristics of a SmA - SmC transition following the de Vries asymmetric diffuse cone (ADC) model in which the non-zero director tilt in SmC arises through an ordering of tilting directions rather than an actual increase in average molecule tilt <theta(mol)>. In W504 a small increase in <theta(mol)> of about 4 degrees is however detected in the SmC phase. Although the increase in molecule inclination is much less than the increase in director tilt h, saturating close to 30 degrees, it leads to a shrinkage of the smectic layers by about 1 angstrom, a result of the large initial molecule tilt in the SmA phase, <theta(mol)>(SmA) approximate to 30 degrees. The tilting transition in W504 is thus mainly an ADC model disorder - order transition, but it also has a component of a structural transition. The semi- fluorinated molecular structure of W504 leads to a very weak electron density modulation along the layer normal, giving a vanishing form factor in bulk samples which exhibit no (001) X-ray scattering peak. In thin films the (001) peak is however observed, indicating that the electron density modulation is enhanced by the breaking of the head - tail symmetry of the liquid crystal phase at the LC - air interface. [less ▲]

Electrolyte effects on the nematic-isotropic phase transition in lyotropic liquid crystals

in Liquid Crystals (2005), 32(10), 1301-1306

A phenomenological approach to the description of the electrolyte effect on the nematic– isotropic phase transition in lyotropic liquid crystals is proposed. The influence of the electrolyte is discussed ... [more ▼]

A phenomenological approach to the description of the electrolyte effect on the nematic– isotropic phase transition in lyotropic liquid crystals is proposed. The influence of the electrolyte is discussed by varying the coupling between the concentration variables and the orientational order parameter. The analysis shows that the discontinuity in the first order nematic–isotropic phase transition as measured by TNI{T0 increases as a function of the NI weight fraction of the electrolyte. Here TNI is the first order nematic–isotropic phase transition temperature and TN0I is the extrapolated supercooling limit. The electrolyte dependence of the Cotton–Mouton coefficient and the non-linear dielectric effect in the isotropic phase above the nematic–isotropic phase transition are calculated. The theoretical predictions are found to be in good agreement with experimental results. [less ▲]

On the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal

in Liquid Crystals (2004), 31(9), 1175-1184

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle ... [more ▼]

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A (SmA) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C (SmC) and smectic C-a (SmCa) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC phase, the distribution is biased such that the molecular tilt already present in SmA now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmCa is about 20degrees larger than in SmA. The large optical tilt (45degrees) in the SmCa phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations. [less ▲]

Phases, phase transitions and confinement effects in a series of antiferroelectric liquid crystals

in Liquid Crystals (2002), 29(2), 163-178

Using a variety of optical and electrooptical techniques as well as dielectric spectroscopy, we have investigated three homologues in the chiral liquid crystal series nF1M7, where n denotes the length of ... [more ▼]

Using a variety of optical and electrooptical techniques as well as dielectric spectroscopy, we have investigated three homologues in the chiral liquid crystal series nF1M7, where n denotes the length of the unbranched side-chain. The main focus of the study is the series of smectic C subphases, i.e. SmCa*, SmC1/3* and SmC1/4*. During switching in the SmCa* phase, a peculiar redirection of the plane of biaxiality, distinguishing this phase from SmA* and SmC*, was observed. We present a simple explanation for this behaviour which correlates well with the clock model description of the SmCa* phase. We found a zero mesoscopic polarisation for the SmC1/4* phase and a non-zero mesoscopic polarisation for SmC1/3*, observations which are consistent with a distorted clock model. The dielectric spectroscopy investigations, performed at several different cell gaps, clearly show that the dielectric response in these materials is easily dominated by surface-induced structures if the cell gap is reduced, and thus reflects the bulk thermodynamic phase in very thick cells only. [less ▲]