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.     

Polymer-stabilized cholesteric liquid crystal microgratings: a comparison of polymer network formation and electro-optic properties for mesogenic and non-mesogenic monomers

Polymer-stabilized liquid crystal microgratings are made using a focused Gaussian UV laser beam to photopolymerize 3 wt % reactive monomer in a cholesteric liquid crystal host. In a typical case, round gratings of 300 μm diameter and 10 μm pitch are produced. The microgratings highlight interesting differences between mesogenic and non-mesogenic monomers in the assembly and spatial distribution of polymer networks formed in a cholesteric host. We also observe a corresponding variation in the electro-optical properties of the stabilized gratings. In the mesogenic case, the grating state of the liquid crystal is faithfully captured even for relatively short UV exposures and over regions only a few pitch lengths in size. These findings are consistent with phase separation of the mesogenic monomer into regular domains templated by periodic, macroscopic variations in orientational order of the host. This templating effect is significantly reduced in the non-mesogenic case.     

New hydrogen-bonded comblike polyimides with mesogenic side chains for stable orientation and fast switching of liquid crystals

ABSTRACT

New supramolecular comblike polyimides with mesogenic side chains for stable homeotropic orientation and fast electro-optical switching of liquid crystals (LCs) have been prepared through selective intermolecular hydrogen bonding between 4-(4-heptylphenyl)benzoic acid (4HPB) and host polyimide. A low concentration of 4HPB as the mesogenic guest molecule was hydrogen-bonded to polyimide backbone leading to the self-assembled comblike polyimide with enhanced homeotropic orientation properties. The electro-optical characteristics of the LC device containing hydrogen-bonded comblike polyimide exhibited better performance than those of LC cell with conventional polyimide. Because the conventional covalent approach for preparation of polyimides requires considerable synthetic efforts to achieve new functionality in polyimide materials, the proposed noncovalent method is a simple one and highly cost effective. Our controlled methodology should find wide application for the fabrication of functional alignment materials requiring high orientation ability.     

Size control of phase‐separated liquid crystal droplets in a polymer matrix based on the phase diagram

When a mixture of liquid crystal (LC) and photo reactive monomer is irradiated by UV light, polymerization occurs and LC droplets form through phase separation, producing polymer dispersed LCs (PDLCs). Although size control of LC droplets and reduced amounts of LC in PDLC films are important in applications, precise size control of LC droplets at a low LC fraction has not yet been accomplished. In this study, the phase diagrams of the LC/initial monomer and the LC/polymer during polymerization were used to control LC droplet size at various LC fractions. Both the relative position of the sample in the initial phase diagram and the shift of the phase separation line during polymerization were shown to be important in determining the size of LC droplets. Our results are expected to provide a new strategy for precise size control of LC droplets especially at a low LC fraction range, which would be a great help for PDLC applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Polymer-stabilized cholesteric liquid crystal microgratings: a comparison of polymer network formation and electro-optic properties for mesogenic and non-mesogenic monomers

Polymer-stabilized liquid crystal microgratings are made using a focused Gaussian UV laser beam to photopolymerize 3 wt % reactive monomer in a cholesteric liquid crystal host. In a typical case, round gratings of 300 μm diameter and 10 μm pitch are produced. The microgratings highlight interesting differences between mesogenic and non-mesogenic monomers in the assembly and spatial distribution of polymer networks formed in a cholesteric host. We also observe a corresponding variation in the electro-optical properties of the stabilized gratings. In the mesogenic case, the grating state of the liquid crystal is faithfully captured even for relatively short UV exposures and over regions only a few pitch lengths in size. These findings are consistent with phase separation of the mesogenic monomer into regular domains templated by periodic, macroscopic variations in orientational order of the host. This templating effect is significantly reduced in the non-mesogenic case.     

New isothiocyanato liquid crystals containing thieno[3,2-b]thiophene central core

New isothiocyanato liquid crystal (LC) materials based on thieno[3,2-b]thiophene core have been synthesised and characterised. Their mesomorphic and physical properties were evaluated. The results indicate that most of the new compounds exhibit only enantiotropic smectic A phases with high clearing points, and the difluorinated compounds (A3 and A6), in particular, also display a stable nematic phase with low melting points. Compared with the corresponding biphenyl and thiophene-phenyl analogues, these thieno[3,2-b]thiophene-based compounds possess increased birefringence (the highest value found to be 0.40) and mesogenic phase intervals. These new thieno[3,2-b]thiophene-based LCs exhibit a high birefringence and a high clearing point and are of potential use as components of high birefringence mixtures.     

Cyano terminated tolane compounds for polymer dispersed liquid crystal application: relationship between cyano terminated tolane based molecular structures and electro-optical properties

ABSTRACT

The structures of the liquid crystal (LC) molecules have a key role in impacting the electro-optical performance of a polymer dispersed liquid crystal (PDLC) film. In this paper, the relationship between the LC molecular structures and the electro-optical properties of PDLC films is investigated based on an unexplored cyano-terminated tolane compounds (CTTCs) doped E8 LCs/UV polymers system. Due to the high polarity of CTTCs, LCs doped with the cyano-terminated tolane (CTT) molecules exhibit high birefringence and large positive dielectric anisotropy. On the whole, PDLC films doped with the CTT molecules exhibit a lower driving voltage than that doped with the pure E8. More excitingly, PDLC films based on CTT molecules with larger length-to-width ratio and longer conjugated system show higher contrast ratio (CR) and faster response time. Eventually, the mechanism of the effects of CTT-based molecular structures and the relationship between the electro-optical performance of PDLC films and CTT molecules are illustrated. This work paves a new way for optimising the electro-optical properties of PDLC films.     

Electrooptical properties of new type fluorinated phenyl-tolane isothiocyanate liquid crystal compounds

A series of 4?-(4-alkyl-phenyl)-2?,6?-difluorotolane isothiocyanate liquid crystal (LC) compounds were synthesised, and their phase transitions and electrooptical properties were investigated. These compounds exhibit high birefringence, about 0.47–0.52. As the number of carbon atoms in the alkyl chains increases, these LC compounds can exhibit smectic phases. When these LCs were mixed into the commercial LCs, the birefringence values of LC mixtures become higher than pure commercial LCs, and the visco-elastic coefficients of five LC mixtures are very close to each other at every test temperature. The results of response properties indicate that the compounds with a tri-fluorine substitution and n-propyl end group possess better response performance than the others. These LC compounds are particularly attractive for achieving fast response times in LC optic devices.     

Reversible Photoresponsive Molecular Alignment of Liquid Crystals at Fluid Interfaces with Persistent Stability

This work demonstrates a noninvasive approach to control alignment of liquid crystals persistently and reversibly at fluid interfaces by using a photoresponsive azobenzene‐based surfactant dissolved in an ionic liquid (IL), ethylammonium nitrate (EAN). As the first report on the orientational behavior of LCs at the IL/LC interface, our study also expands current understanding of alignment control of LCs at the aqueous/LC interface by adding electrolytes into aqueous solutions. The threshold concentration for switching the optical responses of LCs can be changed just by simply manipulating the ratio of EAN to H₂O. This work will inspire fundamental studies and novel applications of using the LC‐based imaging technique to investigate various chemical and biological events in ILs.     

Phase behaviour of mixtures of side-chain LC polyoxetanes with E7 and their field response

We prepared and characterized a series of side-chain liquid crystalline (LC) homo- and copolyoxetanes containing varying fractions of the mesogenic 4-decyloxy-4'-cyanobiphenyl pendent and the non-mesogenic propoxy group. The miscibility of homo- and copolyoxetanes (Co-LCPs) with E7 also was studied. The LC properties of the Co-LCP/E7 mixtures were unique in that, although E7 is a nematic mixture, all the Co-LCP/E7 mixtures form layered smectic mesophases. Among the mixtures, the composition of 30 wt % of LCP bearing 16 mol. % of the mesogenic pendant, Co(16)-LCP, and 70 wt % of E7 formed the smectic phase over a broad range of temperature (-70 to 35°C), although the isotropization temperature of Co(16)-LCP itself was below room temperature. A flexible plastic display was constructed utilizing this mixture and its display characteristics were evaluated. For a device with a 10 µm thick active layer, the threshold voltage was about 30 V and exhibited a rising response time of 200 ms. The most remarkable observation made was that the blends revealed excellent memory behaviour.     

Improvements in morphological and electro‐optical properties of polymer‐dispersed liquid crystal grating using a highly fluorine‐substituted acrylate monomer

To improve the morphological and electro‐optical properties of a polymer‐dispersed liquid crystal (PDLC) grating, a type of highly fluorine‐substituted acrylate monomer was added to the prepolymer mixture. The morphologies of the PDLC gratings were investigated using atom force microscopy and scanning electron microscopy. The grating had a very clear polymer/LC interface after addition of 3.9 wt % of fluorine‐substituted monomer. The LC droplets in this case were much larger than the sample without fluorinated monomer. This phenomenon indicated that an almost complete phase separation had occurred. However, as the content of fluorine‐substituted monomer increased, the morphologies of gratings became less defined and the volumes of LC droplets were smaller. The diffraction efficiency (DE) decreased with increasing of fluoride content and the V ₉₀ increased simultaneously, which may be ascribed to the blurry interface and the small LC droplets. The highest DE (90%) and lowest V ₉₀ (70 V) were obtained simultaneously under the condition of 3.9 wt % fluoride added in the prepolymer. In addition, it was also found that the fluorine‐substituted monomer may disorder the alignment of LCs in the grating.     

Non-symmetric chiral nematic liquid crystal dimers containing trifluoromethyl and 1,2-propanediol

ABSTRACT

A series of non-symmetric liquid crystal (LC) dimers with the same chiral core 1,2-propanediol (PD) have been synthesised, termed as ABBA-PD-TFBA, PBBA-PD-TFBA, ABA-PD-TFBA, PBA-PD-TFBA and AA-PD-TFBA, respectively, in which one of the two mesogenic groups, the fluorinated mesogenic unit, was kept fix and the other arm was different. The intermediate compounds and LC dimers were characterised by FTIR, ¹H NMR, differential scanning calorimetry, thermogravimetric analysis, polarised optical microscopy and X-ray diffractometer (XRD). The results of the measurements indicated that ABBA-PD-TFBA, PBBA-PD-TFBA and ABA-PD-TFBA displayed optical activity and enantiotropic chiral nematic phase, and PBA-PD-TFBA was an enantiotropic nematic LC while AA-PD-TFBA was a monotropic LC, displaying both nematic phase and smectic A phase on cooling. The results indicated that PD was able to induce the chiral nematic phase, nevertheless, the rigidity of the mesogenic arm, the flexibility of the terminal group and even the type of the terminal chemical bond played an important effect on the thermal properties of the dimers, and even on the formation of the chiral nematic phase. It is also worth noting that C=C at the terminal helped to stabilise the LC phase.     

Effects of the structures of epoxy monomers on the electro-optical properties of heat-cured polymer-dispersed liquid crystal films

Polymer-dispersed liquid crystal (PDLC) films were prepared from thermal polymerisation-induced phase separation in heat-curable monomers/nematic liquid crystal (LC) mixtures. For PDLCs with a certain amount of LCs, the microstructure and the refractive index of polymer networks could be influenced by the relative content of epoxy monomers, owing to their different chemical structures. The effect of these factors on the electro-optic properties of films was also investigated.     

In situ self-assembled photo-switchable liquid crystal alignment layer using azosilane monomer-liquid crystal mixture system

Self-assembled monolayers (SAMs) are a unique approach for the liquid crystal (LC) alignment in electro-optical applications such as displays. Herein, a new methodology for photo-switchable LC alignment layer using an azosilane monomer and LC mixture system in the absence of any other foreign alignment layer is presented. The azosilane monomer spontaneously separated from the host LCs, and formed a stable monolayer network on the substrate surface. Data from X-ray photo-electron spectroscopy (XPS), spectroscopic elipsometry (SE), water contact angle and LC alignment studies confirmed that, in the azosilane and LC mixture system, azosilane makes an in situ SAM that is capable of photo-switchable LC alignment layer on glass and indium tin oxide (ITO) substrates. The LCs are aligned with respect to change in the photo-isomerisation of the azo molecule.     

Nematic nanocomposites with enhanced optical birefringence

The proper performance of electro-optical devices utilising liquid crystals (LCs) requires materials with high diffraction efficiency, i.e. with high optical/dielectric anisotropy, low threshold voltage and fast switching. One can achieve increase of dielectric anisotropy by using chemical synthesis or mixing LC materials. However, in most cases, this causes an increase in the threshold voltage and switching times. Therefore obtaining materials with high dielectric anisotropy and keeping threshold voltage and switching times low is a challenging task. We achieved promising results by making binary mixtures of a polar nematic LC 4'-hexyl-4-biphenylcarbonitrile (HBPCN) with low percentage (1–10% by weight) gold nanoparticles. We report that for the mixtures with 1% and 2% gold the dielectric anisotropy increases by 100% and the birefringence by about 50% of their values for pure nematic. We also report that the increase of the dielectric anisotropy in the mixtures only slightly affects threshold voltage and switching times. We propose that this increase is caused by cluster formation in the mixtures.     

Morphology,electro-optical and dielectric properties of polymer network liquid crystals in visible wavelengths

The correlations among electrical, optical properties and polymer morphologies of polymer network liquid crystals (PNLCs) constructed with various curing parameters are investigated. The experimental results indicate that high UV curing intensity, low curing temperature and high monomer-dopant concentration reduce the sizes of liquid crystal (LC) domains, thereby decreasing field-off response time and light scattering and increasing phase retardation of the PNLC cells. Photoinitiator concentration affects the LC domain size as well. For instance, increase in photoinitiator concentration results in the acceleration of polymerisation and thus decreases LC domain size. This effect increases driving voltages of the PNLC cells. Notably, excessive amounts of photoinitiator increases the LC domain size of the PNLC cell. Furthermore, dielectric measurement reveals that decrease in the LC domain size generally increases the dielectric relaxation frequency of the PNLC cells. When the LC domain size is small enough, the dielectric relaxation frequency of the PNLC cell is further dominated by the monomer concentration owing to the increased densities of polymer networks that facilitate the alignment of LC molecules.     

Anisometric,non-mesogenic,tailor-made monomer for reverse-mode shutters

Reverse-mode operation films can be achieved with polymer dispersed liquid crystals by many methods. One method consists in the use of either rough or polyimide treated supports in order to induce homeotropic alignment of the initial mixture that will separate in liquid crystal and polymer rich phases. The major disadvantage is the need for mesogenic monomers to keep a good alignment of the liquid crystal after the polymerization process. In this paper we present results concerning the use of an anisometric, non-mesogenic, tailor-made monomer for the preparation of excellent reverse-mode polymer dispersed liquid crystal shutters cast on rough surfaces. The combined use of rough surfaces and non-mesogenic monomers allows us to exceed earlier limits in physical and chemical properties, cost, and device dimensions by the use of a wider class of monomer molecules.     

Morphology of polymer networks polymerized in highly ordered liquid crystalline phases

The morphology and optical properties of polymer stabilized liquid crystals formed in a more highly ordered low molecular weight liquid crystal solvent were studied. Tetrafunctional, mesogenic monomers (with and without flexible spacers) were polymerized in isotropic, nematic and smectic phases of the LC solvent (4′-octyl-4-cyanobiphenyl) and studied with scanning electron microscopy and cross-polarized light microscopy. The network morphology of the nematic and isotropic phase polymerizations showed strong similarities with the corresponding polymerizations in other solvents. Polymerization in the smectic phase, however, resulted in marked increases in network order and directionality. Most dramatically, even the polymer without flexible spacer formed a fibrous network of rodlike units, in contrast to the random, beaded texture formed by the same polymer in nematic or isotropic conditions. Correspondingly, a large increase in birefringence demonstrated significant polymer orientation and more effective orientational interaction with the liquid crystalline solvent.     

An electrically controlled light-scattering device based on liquid crystal/polymer microsphere composites

ABSTRACT

There is a widely applied prospect of electrical controlled liquid crystal (LC) light-scattering device. Numerous electrical controlled LC light-scattering technologies have been studied, but each technology has its own shortcomings, such as high driving voltage, high hysteresis, complex electrode structure, and serious heating. In this work, the composite of LC and polymer microspheres are used to fabricate light-scattering devices. This device is operated by the vertical electric field and does not require complex preparation process. LC/polymer microsphere composite has the advantages of low driving voltage and zero hysteresis. The role of microspheres in the composites is to change the size and density of a refractive-index-mismatched micro-domain. The effects of the ratio, particle size, and refractive index of microspheres on the optical characteristics of a composite are studied. The normal directional light transmittance at the transparent state and light-scattering state decreases with an increasing weight ratio of microspheres. The particle size of microspheres has negligible influence on the electro-optical properties of composites when the weight ratio of microspheres is small. The LCs doped with Polymethylsilsesquioxane (PMSQ) microspheres or polymethyl methacrylate (PMMA) microspheres are compared, and the mismatched refractive index and density of micro-domain show the influence on the electro-optical properties of the composites.     

V-shaped Schiff’s base liquid crystals based on resorcinol: synthesis and characterisation

ABSTRACT

This paper designed and synthesised a series of V-shaped liquid crystal molecules (X-SBA_nE) with resorcinol as the core and Schiff base as the mesogenic arms (X-SBAA_n). The effects of polarity of terminal groups (X=-CH₃O,-CH₃,-Cl) and length of flexible chain (n = 4,6,8) on mesogenic ranges were discussed. The chemical structure of X-SBAA_n and X-SBA_nE was studied using FT-IR and ¹H-NMR while their thermal behaviour and mesogenic ranges were investigated via differential scanning calorimetry (DSC) and polarising optical microscopy (POM). The results indicated that X-SBAA_n containing OCH₃ and Cl substituents exhibited mesophase except for the analogue having CH₃ substituent which was found to be non-mesogenic. All of the synthesised X-SBA_nE had liquid crystal properties and exhibited nematic phases in heating and cooling. The length of the flexible spacers and terminal groups significantly influenced their mesogenic ranges.