Vitrifying star-shaped liquid crystals: synthesis and application in cholesteric polymer networks

In this paper, the formation of glass-forming reactive mesogens, that do not crystallize upon cooling, but vitrify and form supercooled LC phases, is described. These molecules exhibit broad range LC phases and enable us to carry out photopolymerization in a broad range of temperatures. From such reactive mesogens densely crosslinked networks in which the liquid crystalline order is permanently fixed are formed by photopolymerization. For this purpose eight novel low molecular mass LC materials with photopolymerizable acrylate groups have been synthesized and the detailed experimental procedures are given. The molecules have a star-shaped topology with three and four arms. The mesogenic units were varied by the addition of lateral groups in different positions. Comparing the twin molecules which we have described before with the novel three- and four-armed stars, we found that the supercooled LC phase in the three-armed stars has a stability superior to that in both twin molecules and four-armed stars. In the three-armed star triple-4 with a suitable substituent pattern, the supercooled nematic phase is stable at room temperature for at least nine months. Photo-DSC experiments show that the final conversion after 10 min of UV-irradiation for the threearmed star molecule triple-4 is as high as for the smaller molecules twin-4 and mono-4 over the whole temperature range. Doped with a suitable chiral molecule the novel nematics formed cholesteric phases which were used to make cholesteric polymer networks by photopolymerization.     

Mechanically activated cholesteric polymer dispersed liquid crystals

In this paper we deal with a cellulose derivative cholesteric dispersed liquid crystal (CCDLC) with mechanically tuneable optical properties. The composite is formed with a matrix of acetoxypropylcellulose with embedded micrometric and submicrometric droplets of a cholesteric mixture. Polarizing optical microscopy and atomic force microscopy (AFM) measurements performed on the system are reported and it is shown that the wavelength of the reflected light can be changed by a temperature variation and it is also changeable through a mechanical deformation. The pitch of the deformed droplets can be measured from AFM photographs and compared with the wavelength reflected by the CCDLC composite material.     

Mechanically activated cholesteric polymer dispersed liquid crystals

In this paper we deal with a cellulose derivative cholesteric dispersed liquid crystal (CCDLC) with mechanically tuneable optical properties. The composite is formed with a matrix of acetoxypropylcellulose with embedded micrometric and submicrometric droplets of a cholesteric mixture. Polarizing optical microscopy and atomic force microscopy (AFM) measurements performed on the system are reported and it is shown that the wavelength of the reflected light can be changed by a temperature variation and it is also changeable through a mechanical deformation. The pitch of the deformed droplets can be measured from AFM photographs and compared with the wavelength reflected by the CCDLC composite material.     

Time‐dependent deformation of structurally chiral polymer networks in stabilized cholesteric liquid crystals

Polymerization of crosslinkable liquid crystal monomers in chiral liquid crystalline media stabilizes the phase and enables distinct electro‐optic properties relative to small‐molecule analogs. Particularly interesting are cases where the polymerization forms a crosslinked polymer network that maintains a “structural” chirality. Recent reports have employed this methodology to realize a diverse set of electro‐optic responses in polymer stabilized cholesteric liquid crystals (PSCLCs) including reflection bandwidth broadening, reflection wavelength tuning, and dynamic scattering modes. It has been proposed that the mechanism at the root of these electro‐optic responses is an ion‐mediated, electromechanical deformation of the stabilizing and structurally chiral polymer network. In an effort to better understand the nature of these deformations, here we have characterized the electro‐optic response of PSCLCs with different polymer concentrations and crosslink densities. The dynamic response of PSCLCs to electric fields exhibits a time‐dependent behavior reminiscent of the creep of polymeric materials to mechanical deformations. The electro‐optic response can be described as the superposition of two contributions: the fast deformation of a relatively soft component of the polymer network (1–2 s) and the slower (10–20 s) deformation of a harder component. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1087–1093     

Arch-texture in cholesteric liquid crystals

We have observed an arch-texture in cholesteric liquid crystals sandwiched between two glass plates making a small wedge angle. The anchoring is homeotropic on one plate and planar on the opposite one. This texture is locally periodic and composed of parallel stripes whose average direction rotates by 180° each time the sample thickness increases by p/2, where p is the equilibrium pitch of the cholesteric phase. This texture is due to a periodic modulation of the elastic boundary layer which forms near the plate treated for homeotropic anchoring.     

Cholesteric star-shaped liquid crystals induced by a maltose core: synthesis and characteristics

Three esters of maltose (A1–A3) with 4–(4–(alkoxybenzoyloxy)phenoxy) –6–oxohexanoic acid (b1–b3) side-arms have been synthesised. All the maltose derivatives were laevo-rotationary, unlike their parent cores. The side arm b1 did not display liquid crystalline (LC) properties, and b2 and b3 displayed thermotropic nematic LC properties. The star-shaped compound (SSC) A1 with b1 side-arms did not display a mesomorphic phase. Unlike the nematic schlieren texture provided by side-arms b2 and b3, the star-shaped liquid crystals (SSLC) A2 and A3 displayed Grandjean and oily texture in the cholesteric phase. The results suggest that the LC properties of the side-arms have an important influence on the formation of LC properties in an SSC, and that the maltose core is important in determining the mesomorphic phase type. In other words, the SSC displayed LC properties only when the side-arms were also LC, and the maltose core induced a cholesteric phase in the SSLC with nematic side-arms. The mesomorphic regions for A2 and A3 were 39.1 and 53.7°C during the heating cycle and 63.8 and 107.0°C during the cooling cycle, respectively. The longer terminal chain rendered the mesomorphic region broader.     

Some novel cholesteric liquid crystals

Abstract

We investigate the possibility of inferring the absence of an ordered phase using Monte Carlo simulations. The example we have chosen is that of a one dimensional Lebwohl-Lasher model, where an analytic solution is available. We argue that Monte Carlo can be of help even in this delicate sector notwithstanding the complications created by periodic boundary conditions.     

Some novel cholesteric liquid crystals

A novel series of cholesteric liquid crystals (CNTⁿ). made by quaternization of the new mesogenic unit cholesteryl isonicotinate (CN) with n-alkyl salts, C_nH_2n + ₁ (T) (n = 2 to 8, T = 4-MeC₆H₄SO₃) has been prepared. Differential scanning calorime-try and polarizing optical microscopy studies reveal that all of these salts exhibit an enantiotropic cholesteric phase but for the cholesteryl isonicotinate unit the cholesteric phase is monotropic. For all members of the series the cholesteric-isotropic transitions are not reversible as these salts begin to decompose before their cholesteric-isotropic transition point is reached.     

Effective electrically tunable infrared reflectors based on polymer stabilised cholesteric liquid crystals

Electrically tunable infrared (IR) reflectors based on polymer stabilised cholesteric liquid crystals (PSCLC) have been fabricated. The influence of polymerisation time on bandwidth broadening and response time of the IR reflector was investigated. Such IR reflector can reflect broad band of infrared light from 725 to 1435 nm upon application of a DC electric field, while remaining predominantly transparent in the visible region, with the transmittance in the region of 400–700 nm being above 90%. Bandwidth broadening was induced using low operational power with acceptable switching speeds. Model tests reveal that this IR reflector can effectively control the indoor temperature. The distinct properties of such IR reflector make it a good candidate for smart windows of automobiles and buildings to control interior temperature and save energy.     

Chromaticity of polymer-dispersed cholesteric liquid crystals

The colour producing properties of the polymer-dispersed cholesteric liquid crystal colour display have been measured. We show how the central wavelength of the reflection spectrum depends on the sample voltage, chiral concentration, temperature, and viewing angle. From the reflection spectra we calculate the chromaticity coordinates for two situations and display them on chromaticity diagrams. The results indicate that these new systems may be suitable for the use in multicolour displays.     

Synthesis of diaza-crown-ether cholesteric liquid crystals

Five diaza-crown-ethers were synthesized and four of them shown to have smectic liquid crystalline properties. Their properties were determined by DSC and polarized microscopy. This type of smectogenic diazacrown ether has not been reported so far. A novel lyotropic crown ether liquid crystal was obtained from the thermotropic crown ether liquid crystal 7.     

Dye induced great enhancement of broadband reflection from polymer stabilized cholesteric liquid crystals

A series of polymer stabilized cholesteric liquid crystals (PSCLCs) films were prepared from cholesteric liquid crystal (Ch‐LC) mixtures containing different components such as non‐reactive LC monomer, polymerizable monomer, chiral dopant, dye, and photoinitiator upon polymerization. The influence of the polymerizable monomer and dye of Ch‐LC mixtures on the reflection properties was investigated. The reflection bandwidth for all the samples can be increased by photo‐polymerization, and the network upon polymerization derived from two different polymerizable monomers with both one and two functional groups is more effective than that from one polymerizable monomer for broadening the reflection band. Especially, a dye‐doped Ch‐LC film can reflect incident light with the bandwidth over the wavelength range of 550–2350 nm, which is due to a greater pitch gradient formed inside of Ch‐LC film. The gradient pitch network structure was firstly demonstrated by scanning electron microscopy (SEM) with the film prepared from high diacrylate monomer concentration and subsequently proved by using a wash‐out/refill method. The nematic liquid crystals monomers was infiltrated into the polymer network that was prefabricated by removing the low molar weight LCs from the original PSCLCs film, and SEM exhibited the existence of a pitch gradient across the film thickness. The refilled nematic liquid crystals film showed broadband reflection after polymerzition, too. Copyright © 2011 John Wiley & Sons, Ltd.     

Triphenylene-based discotic liquid crystals: star-shaped oligomers and branched-chain polymers

Liquid crystalline main-chain polymers based on a repeat hexaalkoxytriphenylene moiety have previously been made by the reaction of dihydroxytetraalkoxytriphenylenes with α,ω-dibromoalkanes catalysed by caesium carbonate in N-methyl pyrrolidone. We now show that the molecular weights of these polymers can be increased by adding ?5 wt% of a tribromide (a 1,3,5-trialkoxybenzene or trialkoxymethylbenzene with three ω-bromoalkyl substituents) to the reaction mixture. Studies of model oligomer systems show that, provided the ω-bromoalkyl chains are long enough, the presence of these branching points should not affect the formation of the Col_h mesophase. Indeed, if ?5 wt% of the tribromide is used in the synthesis of the polymer, it remains liquid crystalline. However, if >20 wt% of the tribromide is used, introducing a high degree of branching and cross-linking, the liquid crystal behaviour disappears.     

Organic electroluminescence using polymer networks from smectic liquid crystals

We report the synthesis of a red light-emitting and photopolymerizable smectic liquid crystal (reactive mesogen). We investigate the suitability of polymer networks formed from smectic reactive mesogens for use in organic light-emitting diodes (OLEDs). The use of mixtures of smectic reactive mesogens is shown to lower the processing temperature for the fabrication of OLEDs to room temperature. We also report efficient energy transfer from a nematic polymer network host to a smectic light-emitting dopant and polarized emission from a polymer network formed from an aligned smectic reactive mesogen.     

Bilayer structures in cholesteric, cyclic-siloxane liquid crystals

X-ray diffraction has been used to investigate a series of commercially available liquid crystals based on a cyclic penta(methylsiloxane) with combinations of cholesteryl-4'-allyloxybenzoate and biphenyl-4'-allyloxybenzoate mesogens pendant on the siloxane ring. A lamellar, (smectic-like) structure is indicated in the mesophase and quenched glassy solid state. Extended molecular dimensions of the mesogens generally account for the observed d spacings. The mesogens may interdigitate within lamellae but the packing and extent of interdigitation is dependent on the ratio of cholesteryl to biphenyl mesogens. There is probably also a structural contribution from the nano-aggregated (nano-phase separated), immiscible, siloxane-rich layer delineating the lamellae interfaces as this mesophase shows unusually good definition; diffraction patterns exhibit high order reflections (up to 6th order). The lamellae have a macroscopic helicoidal twist about an axis lying in the plane of the lamellae, a cholesteric supramolecular structure, which derives from the chiral, steroid mesogenic component. Surprisingly, this mesophase composed of low molar mass cyclic siloxanes may be drawn into fibres tens of metres in length, to give a morphology having the lamellae normal to the fibre axis.     

Optical properties of frustrated cholesteric liquid crystals

In a previous article, we proposed a model to explain the unwinding transition in an electric field of a frustrated cholesteric liquid crystal sandwiched between two glass plates imposing a homeotropic anchoring. We found that three distinct solutions exist in materials of negative dielectric anisotropy: first, the homeotropic nematic at small thickness and small voltage, second, a translationally invariant configuration (TIC) at large voltage and, third, the cholesteric fingers. In this article, we study some optical properties of these solutions. We show first that the TIC rotates the polarization of light. Its 'apparent' rotatory power is calculated exactly and is compared with the experimental data when the TIC-nematic phase transition is second order. The agreement between theory and experiment is excellent. We show in particular that there exist discrete values of the voltage for which the TIC has a pure rotatory power. We then calculated the optical contrast of the fingers when they are observed between crossed polarizers. The agreement with experiment is still satisfactory, in spite of the approximate form of the director field chosen to describe the topology of the finger.     

Anomalous light scattering in photonic cholesteric liquid crystals

ABSTRACT

We have carried out polarisation and angle-resolved measurements of the light scattered from photonic cholesteric liquid crystals. Both in samples doped with laser dyes and in inactive (non-doped) samples we have observed pronounced directional dependences of the scattered light, finding angular ranges where the scattering is greatly enhanced and regions where the effect is almost suppressed. Moreover, the total amount of scattered light has also been found to depend strongly on the polarisation and direction of the incident beam. All the results have been interpreted successfully in terms of a simple expression proposed for the scattering cross section, in which the density of states of the ingoing and outgoing beams plays a major role. The expression would be applicable not only to cholesteric liquid crystals but to any one-dimensional photonic material.     

Thermal tuning band gap in cholesteric liquid crystals

The phase of a liquid crystal (LC) changing from a nematic phase to a cholesteric (Ch) mesophase is achieved by adding different ratios of chiral dopants S811. By studying the transmission spectrum, we are able to measure the helical pitch in cholesteric phase. The pitch in the mixtures of nematic E7 and chiral dopants S811 as a function of the concentration of the dopant and temperature is investigated. The sensitivity of the selective reflection notch of the cholesteric phase to the thermal tuning depends strongly on the ratios of the chiral dopants. It reveals that the influence of temperature is more profound for those cholesteric liquid crystals (CLCs) which exhibit smectic A (SmA) at lower temperatures. When fitted using Keating's formula, the helical pitch calculated from our experimental results lies on the predicted curve. Optimised ratios of the mixture CLCs for the optimised reflection band with the specified wavelength ranging from 467 nm to 2123 nm are suggested.     

Surface anchoring energy of cholesteric liquid crystals

ABSTRACT

In this paper, we propose a suitable surface energy expression for cholesteric liquid crystals. We show that there exists a symmetry allowed term for chiral nematics that doesn’t appear in the traditional Rapini-Papoular surface energy form. We discuss some consequences of this new surface anchoring term.     

Effects of polymer network on electrically induced reflection band broadening of cholesteric liquid crystals

The reflection band of polymer stabilized cholesteric liquid crystals with negative dielectric anisotropy can be broadened by DC electric fields, which was ascribed to the pitch gradient caused by the motion of the structural chirality, that is, the polymer network. They systematically varied the mixture components, such as the photo‐initiator concentration, the monomer functionality, and the chiral dopant, to explore their influences on the reflection band broadening behavior. They learned how to control the polymer network morphology and ion density, which in turn determined the reflection bandwidth. By optimizing the mixture, they have greatly enhanced the broadening effect and achieved large bandwidth at low voltages. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 835–846