Evidence for the non-uniform distribution of polymer networks formed in liquid crystal devices

The electro-optic properties of liquid crystal devices are modified by the presence of a polymer network formed by the exposure to UV light of reactive mesogen molecules dissolved within the liquid crystal host. The effect of the polymer network depends on its density, and knowledge of this through the liquid crystal layer is necessary to understand qualitatively, and to model quantitatively, the electro-optic properties of liquid crystal devices containing polymer networks. Various techniques have been used to study the distribution of the polymer network and these show an increased concentration of the network near the surface closest to the UV light. Evidence is presented that the polymer network distribution becomes more uniform when non-UV absorbing liquid crystals are used.     

The electro-optics of nematic liquid crystals stabilized by a polymer network

Samples of nematics stabilized by a polymer network, which are new composite materials, were prepared. A ZhK-1277 nematic composite and a bisphenyl-A-dimethacrylate monomer were used. Polymerization was conducted via UV radiation. The electro-optic properties, i.e., the dependence of transmittance and the turn-on and turn-off times on the electric voltage and layer thickness, of the resulting material and a pure nematic were studied. The experimental results are explained by the domain structure of the nematic in a polymer network, according to which the liquid crystal in an electro-optic cell is composed of oriented domains separated by thin partitions of the polymer. The size of the domain regions of the liquid crystal is 2 μm.     

Polymer network structure and electro-optic performance of polymer stabilized cholesteric textures II. The effect of UV curing conditions

The effect of UV curing intensity and curing time on the electro-optic behaviour and network morphology of reverse mode polymer stabilized cholesteric textures (PSCTs) has been studied. Scanning electron micrographs indicate that increasing the curing intensity generally results in a more open polymer network characterized by a larger average void size, while the morphology of the individual strands remains largely unchanged. In addition, as the polymerization process proceeds, voids within the network are observed to decrease in size. PSCTs with sufficiently large network voids exhibit a two-stage switching behaviour consistent with a model in which the cholesteric liquid crystal is divided between two distinct environments one in which the liquid crystal is strongly dominated by the polymer network, the other in which a bulk-like behaviour, comparable to the unstabilized cholesteric material, is observed.     

Liquid crystal/liquid-crystalline network composite systems Structure formation and electro-optic properties

The supermolecular structure and the electro-optic properties of a composite system consisting of a dense liquid-crystalline network and a low molar mass liquid crystal embedded in the network have been characterized. The composite systems were obtained by a photopolymerization of mixtures of a rigid mesogenic spacerless diacrylate and a low molar mass liquid crystal. They are characterized by a homogeneous distribution of the low molar mass liquid crystal in the network. The network has a cocontinuous periodic spinodal-type structure having a characteristic length scale of the order of 10 nm, if the low molar mass liquid crystal is removed or replaced by other solvents. The electro-optic switching properties are characterized by the fact that the active switching time and the width of the Frederiks transition are shifted to larger values as compared to those of the pure liquid-crystalline state. The decay times, on the other hand, are strongly reduced in the network.     

Liquid crystal/liquid-crystalline network composite systems Structure formation and electro-optic properties

Abstract

The supermolecular structure and the electro-optic properties of a composite system consisting of a dense liquid-crystalline network and a low molar mass liquid crystal embedded in the network have been characterized. The composite systems were obtained by a photopolymerization of mixtures of a rigid mesogenic spacerless diacrylate and a low molar mass liquid crystal. They are characterized by a homogeneous distribution of the low molar mass liquid crystal in the network. The network has a cocontinuous periodic spinodal-type structure having a characteristic length scale of the order of 10 nm, if the low molar mass liquid crystal is removed or replaced by other solvents. The electro-optic switching properties are characterized by the fact that the active switching time and the width of the Frederiks transition are shifted to larger values as compared to those of the pure liquid-crystalline state. The decay times, on the other hand, are strongly reduced in the network.     

PDLC-like patterns at the isotropic to cholesteric transition entrapped by in situ photopolymerization

When investigated by optical microscopy between crossed polarizers, the isotropic to cholesteric transition may appear like fingerprint-patterned droplets embedded in a black isotropic matrix. In the present work, such PDLC-like (polymer dispersed liquid crystal) patterns, only occurring over 0.7 C, have been entrapped and stored at ambient temperature in a polymer film. We used a UV polymerization process with different sequences in which illumination time and UV power progressively vary. From a conceptual viewpoint, these PDLC-like patterns come solely from liquid crystalline material, whereas all the conventional PDLCs are binary mixtures of a macromolecular compound or 'prepolymer' with a conventional low molecular mass liquid crystal. The fact that isotropic matrix and cholesteric droplets differ only from the viewpoint of molecular order and not in their chemical nature, permits comparisons with the usual case for which the choice of polymer-forming material is crucial and the polymer/liquid crystal interface is an important factor for controlling PDLC electro-optic properties. The present system gives an opportunity to investigate by scanning electron microscopy (SEM) the droplet microstructure (isotropic-cholesteric interface, fingerprint patterns or defects), whereas previous SEM studies were focused on the shape and size of empty cavities, since the fluid liquid crystal was inevitably removed from the PDLC system.     

PDLC-like patterns at the isotropic to cholesteric transition entrapped by in situ photopolymerization

When investigated by optical microscopy between crossed polarizers, the isotropic to cholesteric transition may appear like fingerprint-patterned droplets embedded in a black isotropic matrix. In the present work, such PDLC-like (polymer dispersed liquid crystal) patterns, only occurring over 0.7 C, have been entrapped and stored at ambient temperature in a polymer film. We used a UV polymerization process with different sequences in which illumination time and UV power progressively vary. From a conceptual viewpoint, these PDLC-like patterns come solely from liquid crystalline material, whereas all the conventional PDLCs are binary mixtures of a macromolecular compound or 'prepolymer' with a conventional low molecular mass liquid crystal. The fact that isotropic matrix and cholesteric droplets differ only from the viewpoint of molecular order and not in their chemical nature, permits comparisons with the usual case for which the choice of polymer-forming material is crucial and the polymer/liquid crystal interface is an important factor for controlling PDLC electro-optic properties. The present system gives an opportunity to investigate by scanning electron microscopy (SEM) the droplet microstructure (isotropic-cholesteric interface, fingerprint patterns or defects), whereas previous SEM studies were focused on the shape and size of empty cavities, since the fluid liquid crystal was inevitably removed from the PDLC system.     

Formation of a host nanostructure for ferroelectric liquid crystals using thiol-ene polymers

Liquid crystal displays are a subject of intense research interest because of their application to high definition display devices. Recently, polymer stabilized ferroelectric liquid crystals (PSFLCs) have been investigated due to the enhanced electro-optic properties of FLCs. We have utilized thiol-ene photopolymerizations to form a PSFLC system. Thiol-ene photopolymerizations are radical reactions, which proceed via a step growth reaction mechanism. During the polymerization, the polymer network structure is trapped into place due to the rapid transition from low molecular mass monomers and oligomers to high molecular mass polymer. This aspect is evidenced by phase transition data for the FLC, which indicates that the monomer and polymer are not phase separated from the FLC. Infrared dichroism shows that both monomer and polymer are ordered in parallel with the smectic layers of the FLC. Small angle X-ray scattering (SAXS) data show that both monomer and polymer are swelling the smectic layers. Thus, a polymer nanostructure is produced that serves as an ordered, stabilizing host for the FLC.     

The effect of nanographites dispersed in Undec-10-enic acid on optical property and morphology of PDLC films

The electric conductivity is an important factor for reducing the switching voltage of polymer-dispersed liquid crystals (PDLC) films. The electric conductivity of polymer matrix is changed by doped nanographite which is uniform dispersed in polymer matrix in acid condition. The influence of doped nanographite to switching electric field is studied. With increasing of doped nanographite, the switching voltage is dramatically reduced. The effect of nanographite on the polymerization and electro-optic are discussed. The kinetic polymerization of the PDLCs is monitored in lights scattering by UV/VIS spectrometer. The polymerization speed is compared by the max scattering point in different samples which doped by nanographite. The electro-optic of PDLCs films is measured by Polarimeter (PerkinElmer Model 341) to determine the threshold voltage. Information gained from polarizing optical microscope and Fourier transform infrared image depict the morphology of the liquid crystal droplets dispersed in polymer matrix.     

UV tuning of the electro-optical and morphology properties in polymer-dispersed liquid crystals

Polymer-dispersed liquid crystal (PDLC) films operating in reverse mode are transparent electro-optical devices, which can be turned into an opaque state by application of a suitable electric field. The effect was investigated of different UV powers, used during the polymerization process, on the electro-optical and morphology properties of PDLCs, working in reverse mode operation. Films were obtained by UV polymerization of mixtures of a low molecular weight nematic liquid crystal and a photopolymerizable liquid crystal monomer, homeotropically aligned by rough conductive surfaces. The electro-optical and morphology properties of samples were related to the polymerization conditions. Samples polymerized by lower UV powers exhibited “polymer ball” morphology and an electro-optical response due to the liquid crystal director reorientation, whereas samples obtained at higher UV powers showed a “Swiss cheese” morphology and an electro-optical response due to dynamic scattering. In addition, we observed by conductivity and IR measurements that UV exposure induces a degradation of the nematic liquid crystal.     

Polymerization of Blending Cholesteryl Acrylate and Methyl Phenyl Benzoyl Acrylate

Liquid crystal is a material which is between solid and liquid phase and commonly called mesophase. Blends of liquid crystal are of great interest because of their unique optical properties. Blending in this study using two monomers of liquid crystal were cholesteryl acrylate and methyl phenyl benzoyl acrylate. The polymerization process using uv curing techniques by irradiation UV ray and without irradiation UV ray. Polymerization of blending liquid crystal acrylate using initiator 2-hydroxy-2-methyl-1-phenylpropane. Based on peak at GPC curve of polymerization by irradiation UV ray, type of that polymer is copolymer. Therefore the polymerization without UV ray, type of that polymer is homopolymer. SEM images of liquid crystal acrylate polymer showed lamella chain models that are characteristic of a polymer chains. Type of polymer liquid crystal acrylate was the type of Side Chain Liquid Crystalline Polymers (SCLCPs). Therefore acrylate polymer liquid crystal in this research has semi-crystalline phase, which contained crystalline phase and amorphous phase on the XRD pattern. The results of FT-IR spectroscopic characterization of the two monomers showed a peak at the wave number of 1600.43 cm ^-1 and 1622.86 cm^-1 which indicates a double bond (C=C) were obtained from acrylation. While the spectroscopy on the product blending the wave number of the peak regions is reduced that shows that carbon double bonds (C=C) in the acrylate group has polymerized. It also strengthened with a very sharp peak for CC functional groups on the wave number of 2855.15 cm^-1. The results of this study indicate that the liquid crystal polymer acrylic polymerization results with radiation UV ray and without UV ray, respectively absorb light in the UV wavelength region 363 nm and 351 nm.     

Broadband reflective cholesteric liquid crystalline gels: volume distribution of reflection properties and polymer network in relation with the geometry of the cell photopolymerization

The ultraviolet (UV) light‐absorbing properties of the liquid crystal (LC) constituent during the photo‐induced elaboration of a cholesteric LC (CLC) gel may induce the broadening of the reflection bandwidth of the material, a situation that is promoted by asymmetrical irradiation conditions (only one side of the cell is irradiated). The in situ structure of the polymer network, included in the LC, was investigated by transmission electron microscopy and the temperature dependence of the reflection properties examined; it is shown that the network has a structure gradient that is at the origin of the broadening phenomenon. The smallest reflection wavelength is related to the cell side from which the UV light beam came in. A priori, this situation was unexpected since it is shown that this part of the gel is enriched with nematic (infinite‐pitch CLC) network‐forming material. The result is discussed in relation to the variation of the reflection band characteristics with polymer concentration, which offers the opportunity for indirect access to the volume distribution of the cholesteric periodicities. For applications, broadband reflective cholesteric gels may be of interest for reflective polarizer‐free displays or for the light management with smart electrically‐switchable reflective windows.     

Polymer network structure and electro-optic performance of polymer stabilized cholesteric textures I. The influence of curing temperature

The effect of curing temperature on the electro-optic behaviour and network morphology of reverse mode polymer stabilized cholesteric textures (PSCTs) has been studied. Scanning electron micrographs indicate that increasing the curing temperature generally results in a larger average void size within a polymer network, while the morphology of the individual strands (which varies significantly for different monomers) remains largely unchanged. PSCTs with sufficiently large network voids exhibit a two-stage switching behaviour consistent with a model in which the cholesteric liquid crystal is divided between two distinct environments one in which the liquid crystal is strongly dominated by the polymer network, the other in which a bulk-like behaviour, comparable to the unstabilized cholesteric material, is observed.     

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.     

Volume-stabilized ULH structure for the flexoelectro-optic effect and the phase-shift effect in cholesterics

Flexoelectric coupling gives rise to a linear electro-optic response in cholesterics (flexoelectrooptic effect) with a uniformly lying helix (ULH) structure and this electro-optic effect is strongly reliant on the homogeneity and quality of the texture. The ULH structure, unfortunately, is complicated in itself and may be perturbed by factors such as dielectric coupling, surface/liquid crystal interactions and phase transitions, and often there is a tendency for relaxation into the Grandjean texture (standing helix structure) with time. Hence, in order to exploit the flexoelectro-optic effect in cholesterics any instability of the ULH structure must be ruled out. We have overcome these problems by incorporating a polymer network by means of photopolymerization of a reactive monomer added to the cholesteric. The volume stabilized ULH structure still exhibits the flexoelectro-optic effect, it is stable and it is also retained after heating to the isotropic phase and going back to the cholesteric phase. In addition to the flexoelectro-optic mode, the ULH structure is of interest in an electro-optic mode characterized by a pure phase-shift with no change in amplitude (transmittance). This mode, which has obvious applications in spatial light modulators, optical computing devices and electrically controlled kinoforms and phase holograms working without polarizers, is also briefly discussed.     

Optical and electrical control of circularly polarised fluorescence in CdSe quantum dots dispersed polymer stabilised cholesteric liquid crystal shutter

In the present communication, we report on the synthesis and electro-optic investigation of photosensitive CdSe quantum dots (QDs) dispersed polymer stabilised liquid crystal (PSCLC) luminescent gel. The assembly of the fluorescence properties of CdSe QDs facilitate the anisotropy of PSCLC gel and hence manipulates the optical and electro-optic switching properties, which was further investigated using polarised fluorescence spectrophotometer. The circularly polarised fluorescence intensity was tuned electrically so as to affect the orientations of liquid crystal in the helix. It was found that the electro-optic switching behaviour of QDs-doped sample predicts the improvement in threshold voltage and hence makes them applicable for the switchable liquid crystal contrivances with low power consumption.     

Shear aligned polymer dispersed ferroelectric liquid crystal devices

Fast switching liquid crystal devices can be produced by forming a dispersion of ferroelectric liquid crystal droplets in a polymer film. Such PDFLCs have been fabricated using a polymerization-induced phase separation technique involving ultraviolet photopolymerization, during which the film was sheared to obtain a uniform orientation of the liquid crystal medium. These birefringence devices show fast response times (sub-millisecond), optimum tilt angle (22.5°), and good contrast (∼ 30:1) at room temperature, using ferroelectric switching. We studied the tilt angles, response times and contrast ratio as a function of voltage and temperature to determine the effects of the preparation parameters on the electro-optic behaviour of these devices. Using a ferroelectric liquid crystal with long helical pitch, such devices appear to be bistable.     

Effect of monomer concentration and functionality on electro-optical properties of polymer-stabilised optically isotropic liquid crystals

Optically isotropic nature can open a new type of high-performance liquid crystal (LC) displays. The main features emerge from the interaction between LC and polymer network at the interface. At this point, we investigated the influence of cross-linking monomer concentration and functionality on electro-optic properties of optically isotropic liquid crystal (OILC) obtained by polymerisation-induced phase separation method. Interestingly, we obtained a pore-like network structure constructed by highly interlinked polymer beads in acrylate monomers and achieved fast decay response time (0.6 ms). We found that the voltage-dependent hysteresis was mostly eliminated (~0.25%), and the contrast ratio was enhanced (1:1550) for high functional monomers. The result inspires a simple way to optimise the materials to fabricate a high-performance OILC device and it shows high-transparency, low-driving voltage, hysteresis-free and sub-millisecond response time.     

聚合物分散液晶膜

聚合物分散液晶膜是将液晶和聚合物结合,得到的一种综合性能优异的膜材料,液晶分子赋予了聚合物分散液晶膜显著的电光特性,使其受到了广泛的研究,并有着广阔的应用前景。而聚合物作为成膜材料,起着辅助但是重要的作用,其结构和固化过程是影响聚合物分散液晶膜电光特性的重要因素。本文简要综述了聚合物分散液晶膜的制备方法、电光特性的影响因素及研究手段。     

Broadband reflective cholesteric liquid crystalline gels: volume distribution of reflection properties and polymer network in relation with the geometry of the cell photopolymerization

The ultraviolet (UV) light-absorbing properties of the liquid crystal (LC) constituent during the photo-induced elaboration of a cholesteric LC (CLC) gel may induce the broadening of the reflection bandwidth of the material, a situation that is promoted by asymmetrical irradiation conditions (only one side of the cell is irradiated). The in situ structure of the polymer network, included in the LC, was investigated by transmission electron microscopy and the temperature dependence of the reflection properties examined; it is shown that the network has a structure gradient that is at the origin of the broadening phenomenon. The smallest reflection wavelength is related to the cell side from which the UV light beam came in. A priori, this situation was unexpected since it is shown that this part of the gel is enriched with nematic (infinite-pitch CLC) network-forming material. The result is discussed in relation to the variation of the reflection band characteristics with polymer concentration, which offers the opportunity for indirect access to the volume distribution of the cholesteric periodicities. For applications, broadband reflective cholesteric gels may be of interest for reflective polarizer-free displays or for the light management with smart electrically-switchable reflective windows.