Morphological studies of a (self-assembling oil gelator/liquid crystal) composite system

The aggregation structure of a novel (self-assembling oil gelator/liquid crystal) composite was investigated using light scattering studies and morphological observations. The oil gelator forms a self-assembled-networks aggregate in an organic solvent with a low molecular weight liquid crystal (LC). It became apparent from Hv light scattering patterns and polarizing optical microscopy that two types of LC molecular alignments exist in the composite: a random orientation and a spherulite type one in a nematic gel state. Also, optical and atomic force microscopic observations revealed that fibrils which formed bundles in the fibre-like and spherulite-like aggregates, were formed in the composite. The alignment of the liquid crystal molecules was related to the aggregation structure of the self-assembling oil gelator in a liquid crystal gel state.     

Synthesis and mesomorphic properties of chiral fluorinated liquid crystals

Some fluorinated chiral liquid crystals were synthesized and the compounds characterized by IR, ¹H NMR, ¹⁹F NMR and mass spectroscopy and elemental analysis. Their phase transition behaviour was investigated by differential scanning calorimetry and polarizing optical microscopy. Nearly all of the compounds synthesized are liquid crystals with an enantiotropic cholesteric phase. Some of them exhibit a blue phase. Lateral tetrafluoro substitution decreases the clearing point and molecular polarity affects the formation of liquid crystalline phases.     

Optical studies of dynamic director configurations in ferroelectric liquid crystal devices

An investigation into the transmission spectrum of a ferroelectric liquid crystal device is undertaken. This is done both for an initial static state and during a switching process. Comparisons are made between experimental data and theoretical predictions. The dynamic internal director configurations in the device is shown to be consistent with a simple model during both monopolar and bipolar addressing pulses.     

The dielectric relaxation processes in an antiferroelectric liquid crystal under cylindrical confinement

In the cylindrical pore geometry of inorganic Anopore membranes the collective relaxation processes observed in a bulk antiferroelectric liquid crystal change considerably under confinement. The frequency degeneration of the soft and Goldstone modes present at the smectic A* (SmA*)-chiral smectic C (SmC*) phase transition in the bulk phase is removed under geometrical restrictions. The relaxation rate of the soft mode is strongly modified due to the deformation of the smectic layers in the curved geometry of the pores and is superimposed by the molecular relaxation process in the SmA* and SmC* phases. The soft mode in confinement splits into two relaxation processes, which are present through all other mesophases (SmC* and SmC_a*). One of them is nearly temperature independent and slightly decreases in frequency in the SmC_a* phase. This Goldstone-like process can be assigned to the highly deformed helical structure fluctuations. The second one exhibits the characteristic features for the molecular and soft mode relaxation processes depending on the temperature range. The biquadratic and the piezoelectric coupling between the tilt angle and spontaneous polarization are revealed in their temperature dependence.     

Dynamics in ferro- and antiferroelectric phases of a liquid crystal with fluorinated molecules as studied by dielectric spectroscopy

For 1-[3-fluoro-4-(1-methylheptyloxycarbonyl)phenyl]-2-[4-2,2,3,3,4,4,4-heptafluorobutoxybutoxy)biphenyl-4-yl]ethane (1F7), built of chiral molecules, results of dielectric measurements of liquid-crystalline and solid phases are presented. Rich polymorphism of liquid-crystalline (SmC*, SmC*_A and SmI*_A) phases as well as of solid (Cr1 and Cr2) phases were observed down to –130°C. At a frequency range from 0.1 Hz to 3 MHz, the relaxation processes were detected in ferroelectric SmC*, antiferroelectric SmC*_A and highly ordered SmI*_A smectic phases. The mechanism of complex dynamics (moleculear and collective) was identified with the help of the bias field. Vitrification of conformationally disordered crystal phase Cr2 was found in accordance with calorimetric observations.     

Dielectric relaxation spectroscopy and alignment behavior of a polymer‐dispersed liquid crystal and its component materials

The dielectric properties of a polymer‐dispersed liquid crystal (PDLC), a liquid‐crystal (LC) mixture (BL036), and three polymer matrices of PN314 containing different amounts of BLO36 were determined over a range of frequencies and temperatures and, for the LC and PDLC, over a range of voltages leading to homeotropic alignment of the LC. The overall dielectric relaxation process was a weighted sum of contributions from (1) the primary (δ) process in the LC arising from the motions of the dipoles about the short molecular axis and (2) dipole motions in the polymer matrix. The dielectric spectra were determined as a function of frequency, temperature, and, when appropriate, applied voltage. An equivalent electrical circuit was used as a working model to describe the dielectric behavior of the PDLC in the absence and presence of applied voltages. Agreement between the dielectric data and this model was achieved if a portion of the LC phase at the interface was assumed to be immobile. The director order parameter for the LC component in the PDLC was determined from dielectric measurements as the material was aligned homeotropically in an applied electric field. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1173–1194, 2001     

Dielectric relaxation spectroscopy and electro-optical studies of a new,partially fluorinated orthoconic antiferroelectric liquid crystal material exhibiting V-shaped switching

In this paper we report the results from detailed electro-optical and dielectric studies in various antiferroelectric and ferroelectric phases of an orthoconic antiferroelectric liquid crystal (OAFLC) material . The material possesses high tilt and high spontaneous polarisation. Such an OAFLC, because of its high tilt, provides an excellent dark state. The material exhibits V-shaped switching in the SmC* phase. Dielectric studies reveal the existence of another phase during heating in the range between 78.6 and 92°C which did not appear in the DSC curve and in polarising microscopy. This phase has been identified as the SmC_γ* phase and is extremely sensitive with respect to the cell conditions, aligning material, purity, etc. Three dielectric modes have been assigned in the above-mentioned temperature range and their origins are discussed.     

Electro-optic effect,propagation loss,and switching speed in polymers containing nano-sized droplets of liquid crystal

Polymers containing droplets of liquid crystal smaller than 100 nm, which have good transparency and easily form films, were prepared under various conditions to evaluate their potential as electro-optic materials for waveguide-type devices. By varying the liquid crystal concentration and the strength of the UV irradiation causing photo-induced phase separation of the droplets, we were able to control the droplet size and density. We have clarified how the birefringence generated in an applied electric field, switching speed, and optical loss of light propagating in the film depend on droplet size and density. Polymer materials having a large electro-optic effect (δn = 0.001 at 8 V μm^-1), low propagation loss (~2.5 dB cm^-1), and fast response time (~10 μs) have been developed.     

Reflective mode of deformed-helix ferroelectric liquid crystal cells for sensing applications

We present a detailed theoretical and experimental study of the reflectance response of a deformed-helix ferroelectric (DHF) liquid crystal (LC) cell to an applied voltage under cross-polarisers. Using a model based on the effective dielectric tensor approximation, we derive simple analytical formulas to design a LC cell with maximum modulation depth and optimal linearity of the electro-optical response intensity versus the electric field. Our experimental results show that the cell works at frequencies up to 10 kHz and exhibits excellent linearity, with a total harmonic distortion as low as ?70 dB. These findings suggest that DHF-LCs can be exploited to develop simple and accurate optical sensors.     

Polymerizable hexacatenar liquid crystals containing a luminescent oligo(p-phenylenevinylene) core

Polymerizable hexacatenar mesogens containing a photo-active oligo(p-phenylenevinylene) core were successfully synthesized by replacing the traditional n-alkoxy tails on the molecules with polymerizable hydrocarbon tails containing terminal isoprenyl or 1,3-dienyl units. It was found that for this particular liquid crystal (LC) platform, the incorporation of conventional radical polymerizable groups such as acrylates in the tails was not conducive to the formation of thermotropic LC phases, presumably due to their polar nature. The resulting photoluminescent isoprenyl and 1,3-dienyl hexacatenar monomers were found to form columnar hexagonal phases at elevated temperatures (c. 45–75°C), as determined by powder X-ray diffraction. Unfortunately, photoinitiated radical polymerization studies revealed that the mesogens are susceptible to photodegradation in the LC state at elevated temperatures, resulting in the loss of both LC order and emission properties during photopolymerization. Thermally initiated radical polymerization in the absence of light, however, afforded effective crosslinking with retention of both LC order and the desired emission properties. The resulting crosslinked columnar hexagonal phases were found to exhibit emission maxima at nearly identical wavelengths, with comparable intensities relative to the unpolymerized starting materials. The effect of the different polymerizable groups on the mesogenic behaviour, polymerization characteristics, and emission properties of the hexacatenar compounds is presented.     

Calorimetric studies of poly (2-phenoxyethylacrylate)/5CB mixtures

The thermophysical properties of mixtures of poly (2-phenoxyethylacrylate) and 4-cyano-4′-pentyl-biphenyl, 5CB, are investigated using polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The polymer has a molar mass M _w = 181 000 g mol ^-1 the low molecular mass liquid crystal exhibits a nematic to isotropic transition at 35.3°C and crystallizes below 23°C. The phase diagram exhibits miscibility gaps in certain regions of temperature and composition where coexisting nematic and isotropic phases are found. From a practical point of view when considering the electro-optical applications of these systems, it proves to be useful to know precisely the amount of small liquid crystal molecules dissolved in the polymer matrix and the concentration of polymer in the nematic phase. The former quantity has a mechanical impact due to a plasticizing effect, an optical impact since it changes the polymer refractive index, while the polymer in the nematic phase shifts the transition temperatures influencing the electro-optical response of the liquid crystal. The present work addresses these important aspects using POM and DSC.     

Polymer and azo-dye composite: a photo-alignment layer for liquid crystals

In this article, we disclose a method to fabricate polymer-stabilised azo-dye photo alignment layers for liquid crystal. The idea includes the introduction of polymer network in the alignment layer, in optimal concentration, followed by two-step irradiation. The stabilised photo-alignment layer has been explored for different aspects of the display-related parameters, viz. anchoring energy, stability for various display-related environments as a function of concentration of monomer and irradiation, residual DC and voltage holding ratio. The composite photo-alignment layer offers well-suited parameters for the liquid crystal alignment and therefore could find application in a variety of modern photonic and display devices.     

Dielectric and electro-optical properties of a photosensitive liquid crystal

The temperature dependencies of the dielectric and electro-optical properties of a pure photo-ferroelectric liquid crystal have been investigated, in the chiral smectic C (SmC*) phase, with and without ultraviolet (UV) illumination. The SmC* dielectric Goldstone mode characteristics, the spontaneous polarization, the tilt angle and the rotational viscosity are affected by UV irradiation. Under increasing UV light intensities the dielectric strength Δ?_G increases whereas the relaxation frequency f_G , the spontaneous polarization P _s, the electro-optical rotational viscosity γ_eo and the tilt angle θ decrease. The twist elastic constant K ₃ and the Goldstone mode rotational viscosity γ_G of the studied compound are deduced from dielectric experimental results. Good agreement was found between both viscosities. The observed dielectric behaviours are controlled by the elastic constant and the rotational viscosity variations.     

Towards a new class of ferroelectric liquid crystal molecules for nonlinear optical applications

The synthesis of a new molecule specifically designed to exhibit both ferroelectric and nonlinear optical properties is presented. This molecule possesses an optically active phenyl sulphinic group, which introduces a dipole moment directly linked to the chromophore group, with a nitro group in the meta -position. The rest of the molecule comprises a tolane and a benzoate group. Such a structure results in an enantiotropic smectic C*-smectic A phase sequence in its polymorphism. A first measurement of the spontaneous polarization shows a high value. The polymorphism of the racemic homologous molecule possessing the nitro group in the ortho-position is also presented, and also shows the smectic C-smectic A phase sequence.     

Morphological studies of a hydrogen-bonded LC polymer obtained by photopolymerization in LC solvents

Anisotropic morphologies and the phase behaviour of a hydrogen-bonded LC polymer obtained by photopolymerization in two kinds of LC solvent are discussed. The hydrogen-bonded LC monomer, 4-(6-acryloyloxyhexyloxy) benzoic acid (A6OBA), was photopolymerized in 4-cyano-4′-hexyloxybiphenyl (6OCB) and in 4-cyano-4′-undecyloxybiphenyl (11OCB), which show a nematic phase and a smectic A phase, respectively. After photo-polymerization, the LC media were removed by extraction and the pure polymer was observed by scanning electron microscopy. SEM images showed that the polymer possessed fibrous morphology with a fibre diameter of a few micrometers, based on polymerization-induced phase separation. The overall geometries reflected typical LC characteristics such as schlieren and focal-conic fan textures. It was found that the hydrogen bond between benzoic acid groups in the monomer was rigid enough to fix the anisotropic phase-separated structure forming during the early stage of phase separation; however, it could not permanently maintain the fibre structure due to dissociation at elevated temperature. X-ray measurements revealed that a well developed layer structure of the hydrogen-bonded mesogen existed in the polymer obtained from the smectic phase of 11OCB, whereas a polymer layer structure could develop only partially from the nematic phase of 6OCB.     

Influence of the remanent polarisation on the liquid crystal alignment in composite films of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and a cyanobiphenyl-based liquid crystal

Polymer-dispersed liquid crystals (PDLCs) of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and nematic 4-cyano-4?-n-hexylbiphenyl (6CB) or 4-cyano-4?-n-pentylbiphenyl (5CB) were prepared to study the effect of the remanent polarisation of the polymer on the liquid crystal alignment. We measured the macroscopic alignment of the liquid crystal molecules in the thickness direction by means of Infrared Transition-Moment Orientational Analysis. Electrical poling at 100 V/µm caused an increased order parameter up to 0.15. After subsequent annealing above the nematic-to-isotropic phase-transition temperature, the order parameter was reduced to 0.02. Nevertheless, the order parameter was still higher than for non-poled film indicating a slight orientation in thickness direction. Both values are lower than those expected from model calculations. In agreement with dielectric measurements, we attribute this result to the shielding effect of mobile charge carriers within the liquid crystal inclusions.     

Low frequency dielectric relaxations of gold nanoparticles/ferroelectric liquid crystal composites

We present the characterisation and dielectric relaxation spectroscopy of a ferroelectric liquid crystal (FLC), namely KCFLC 7S. It was observed that the studied FLC material possesses the tendency of homeotropic alignment on glass substrates coated with indium tin oxide. A low frequency dielectric mode, along with the Goldstone mode, was observed in the SmC* phase of the FLC material. The low frequency mode became more dominant on doping gold nanoparticles into the FLC material. The occurrence of the low frequency mode was attributed to the ionisation–recombination-assisted diffusion of slow ions present in the FLC material. The behaviour of the relaxation frequency of the low frequency mode with applied dc bias and temperature was also demonstrated.     

Low-frequency relaxation modes in ferroelectric liquid crystal/gold nanoparticle dispersion: impact of nanoparticle shape

Low-frequency (1 mHz–100 Hz) dielectric relaxation modes were experimentally studied in ferroelectric liquid crystal (FLC)/gold nanoparticles (nanospheres and nanorods) dispersion. It was demonstrated that the dielectric spectra of nanodispersion are strongly influenced by the shape of nanoparticles. Using different formalisms of the impedance spectroscopy, three possible low-frequency relaxation processes were found in the dispersions and the pure FLC. Due to the electrical double layers (EDLs) near nanoparticles and the alignment layers, one can observe the relaxation of the EDL polarisation around the nanoparticles (Schwarz’s relaxation) and near the driving indium tin oxide (ITO) electrodes (electrode polarisation). The other possible relaxation process is interfacial polarisation (Maxwell–Wagner mode) in which the frequency is unaffected by the nanoparticles. It was shown that Schwarz’s relaxation frequency strongly depended on the shape and size of the nanoparticles. Moreover, dispersion of nanoparticles significantly reduced direct current conductivity of the FLC mixture.     

Enhanced dielectric and electro-optical properties of a newly synthesised ferroelectric liquid crystal material by doping gold nanoparticle-decorated multiwalled carbon nanotubes

In this article, a newly synthesised ferroelectric liquid crystal (FLC) material, namely LAHS 22, has been characterised. The characterisation of the FLC material has been performed using dielectric relaxation spectroscopy, differential scanning calorimetry and polarisation optical microscopy. We observed an enhancement in the dielectric and electro-optical properties of the FLC material by incorporating gold nanoparticles (GNPs)-decorated multiwalled carbon nanotubes (MWCNTs). The GNPs-decorated MWCNTs cause an increment in dielectric dispersion (up to kHz), absorption, spontaneous polarisation and rotational viscosity of the FLC material. The pure and GNPs-decorated MWCNTs doped FLC cells were analysed by means of various dielectric spectroscopic and optical measurements. The observed enhancement in the dielectric and electro-optical properties of the FLC material has also been studied with concentration of GNPs-decorated MWCNTs in FLC material. The GNPs-decorated MWCNTs/FLC composites are not only of fundamental importance, but also useful materials for device applications such as liquid crystal displays and memory devices.     

Antiferroelectric phase in liquid crystalline compounds containing an azo group in their molecular core

Novel lactic acid derivatives containing an azo group in their molecular core have been synthesised and their mesomorphic properties established. Compounds with a short aliphatic non-chiral chain exhibited the SmA* phase and ferroelectric (FE) SmC* phase. The monotropic antiferroelectric (AF) phase was found in the homologues with a longer terminal chain. Spontaneous polarisation and tilt angle were measured for the FE and AF phases. Dielectric spectroscopy in the frequency range 1 Hz–10 MHz was carried out and dielectric properties established within the temperature range of the smectic phases. Two high frequency modes were detected in the AF phase. Small-angle X-ray measurements were conducted, and the temperature dependence of layer spacing values is established and discussed.