Low Molecular Liquid Crystals Research Articles

Effects of dye doping on electro-optical, thermo-electro-optical and dielectric properties of polymer dispersed liquid crystal films

In this study, polymer dispersed liquid crystal (PDLC) films comprising a phase separated low molecular weight thermotropic liquid crystal (LC) and high molecular weight polymer were, prepared using the polymer–induced phase separation method. In order to enhance the optical efficiency of the PDLC films, LC was doped with dichroic azo dye. Various characterization techniques were employed to determine the properties of the components and, the operating principles of the dye–doped PDLC (DPDLC) films. Morphological studies using polarizing optical microscopy and scanning electron microscopy indicated that the LC droplet configuration changed with various dye concentrations and voltages. Electro-optical analysis showed that the performance of the DPDLC film with a low dye concentration (0.007%) was excellent, with a high contrast ratio (241) and transmittance difference (ΔT = 98.57%), low threshold (VTH = 0.85 V/μm) and saturation voltages (VSAT = 1.45 V/μm), and a minimum hysteresis effect. The effects of temperature on the electro-optical properties of the DPDLC films were studied. Absorbance analyses were conducted using ultraviolet–visible spectrophotometry to complement the transmittance analyses. Dielectric relaxation spectroscopy was employed to measure relaxation frequency/time of DPDLC films. Debye and Cole – Cole modeling were conducted to understand nature of the relaxation process. The zero values of the distribution parameter (α) for all of the DPDLC composite films confirmed their Debye type relaxation process.

Paintable Encapsulated Body-Temperature-Responsive Photonic Reflectors with Arbitrary Shapes

A temperature-responsive photonic coating on a flexible substrate was prepared by a photoinduced phase-separation process. In this coating a low molecular weight cholesteric liquid crystal (Ch-LC) mixture was encapsulated between the substrate and an in situ formed protective polymer top layer. The photonic coating showed a blue-shift of the photonic reflection band of 100 nm by heating from 22 to 23 °C due to the close proximity to the smectic to cholesteric phase transition and an overall 330 nm blue-shift while heating from 22 to 45 °C. Hence, the red coating turned green upon contact with skin within seconds. Furthermore, the coating structure and composition were investigated in detail, revealing a thick top coat. The adhesion of the coating was improved by providing trays on the substrate (by etching or 3D printing), resulting in a link between arbitrary-shaped substrates and the protective polymer top layer. These bendable coatings could be of interest for sensors, anticounterfeit labels, or custom...

Photoresponsive Chiral Dopants: Light‐Driven Helicity Manipulation in Cholesteric Liquid Crystals for Optical and Mechanical Functions

AbstractThis Review focuses on recent advancements regarding the design of photoisomerizable chiral dopants which can switch the helical orientation in cholesteric liquid crystals upon light stimuli. Chiral dopants exhibiting conformational change in response to an external stimulus can provide dynamic control of the cholesteric pitch. Development of such responsive systems has been attempted since the 1970s. However, major advances on efficient chiral dopants exhibiting either high helical twisting power or large photoswitching have been achieved only in recent years. This Review covers photoresponsive low molecular weight cholesteric liquid crystal systems based on chiral dopants capable of photochemically “switching power to twist” surrounding liquid crystalline host molecules, “inverting” their handedness or even “inducing” helical organization from the racemic nematic phase.

Shear flows of low molecular weight nematic liquid crystals between parallel circular plates

Shear flows of low molecular weight nematic liquid crystals between parallel circular plates

Micro-Segregated Liquid Crystal Haze Films for Photovoltaic Applications: A Novel Strategy to Fabricate Haze Films Employing Liquid Crystal Technology.

Herein, a novel strategy to fabricate haze films employing liquid crystal (LC) technology for photovoltaic (PV) applications is reported. We fabricated a high optical haze film composed of low-molecular LCs and polymer and applied the film to improve the energy conversion efficiency of PV module. The technique utilized to fabricate our haze film is based on spontaneous polymerization-induced phase separation between LCs and polymers. With optimized fabrication conditions, the haze film exhibited an optical haze value over 95% at 550 nm. By simply attaching our haze film onto the front surface of a silicon-based PV module, an overall average enhancement of 2.8% in power conversion efficiency was achieved in comparison with a PV module without our haze film.

Optical reversible behavior of poly(ethylene-b-ethylene oxide) block copolymer dispersed liquid crystal blends

Optical properties of novel polymer dispersed liquid crystal (PDLC) blends based on two different low molecular weight nematic liquid crystals, 4′-(hexyloxy)-4-biphenylcarbonitrile (HOBC) and N-(4-ethoxybenzylidene)-4-butylaniline (EBBA), and poly(ethylene-b-ethylene oxide) block copolymer (PE-b-PEO), were studied to develop optically reversible PDLC blends applying a temperature gradient. Differential scanning calorimetry (DSC) showed that the liquid crystals, HOBC and EBBA, maintain their nematic-isotropic transition in designed PDLC blends, which was visualized by optical microscopy (OM). Results obtained using photoluminescence and UV–vis spectroscopies indicated that HOBC and EBBA liquid crystals maintain their reversible optical behavior passing from opaque to transparent state when temperature gradient was applied. The reversible switching process was proved in four consecutive heating/cooling cycles. Designed thermo-responsive PDLC blends possessed interesting optical properties, which make them potential candidates to be use as temperature sensors or thermo-optical devices.

Optical sensor platform based on cellulose nanocrystals (CNC) – 4′-(hexyloxy)-4-biphenylcarbonitrile (HOBC) bi-phase nematic liquid crystal composite films

The preparation of composite materials has gained tremendous attention due to the potential synergy of the combined materials. Here we fabricate novel thermal/electrical responsive photonic composite films combining cellulose nanocrystals (CNC) with a low molecular weight nematic liquid crystal (NLC), 4′-(hexyloxy)-4-biphenylcarbonitrile (HOBC). The obtained composite material combines both intense structural coloration of photonic cellulose and thermal and conductive properties of NLC. Scanning electron microscopy (SEM) results confirmed that liquid crystals coated CNC films maintain chiral nematic structure characteristic of CNC film and simultaneously, transversal cross-section scanning electron microscopy images indicated penetration of liquid crystals through the CNC layers. Investigated composite film maintain NLC optical properties being switchable as a function of temperature during heating/cooling cycles. The relationship between the morphology and thermoresponsive in the micro/nanostructured materials was investigated by using transmission optical microscopy (TOM). Conductive response of the composite films was proved by Electrostatic force microscopy (EFM) measurement. Designed thermo- and electro-responsive materials open novel simple pathway of fabrication of CNC-based materials with tunable properties.

Induction of chiral phases in originally achiral hydrogen-bonded dimer liquid crystals

ABSTRACTWe investigated the seventh homologues of the hydrogen bonded in dimers liquid crystals p,n alkyloxybenzoic acids (7OBA), which in its pristine state displays achiral nematic (N) and smectic C (SC) states. The mixture of this liquid crystal with nanoparticles, expressing various shapes and sizes, where the liquid crystal serves as a matrix, introduces new optical and electrooptical properties of the composite material. We concentrated on the mixture 7OBA with single wall carbon nanotubes (SWCNTs), which exposes a set of chiral and ferroelectric states, including the unique one (smectic CG) state, which do not appear in the pristine achiral 7OBA. On the base of polarization microtextural, thermal and polarization spectroscopic (FT far infra red-FT FIR and microRaman) analyses we present a qualitative model of the smectic CG state in low-molecular dimeric liquid crystals.

Photoresponsive Fiber Array: Toward Mimicking the Collective Motion of Cilia for Transport Applications

Remote transport of material is an utmost useful, but challenging, property expanding the design possibilities of many applications such as microfluidics or robotics where species can be carried without interfering with its environment. Nature has solved the problem of transport in e.g., the respiratory system by a concerted motion of cilia. This study addresses a new method to fabricate an array of small parallel fibers acting as cilia placed side by side on a substrate. The fibers consist of a crosslinked liquid crystal main chain polymer functionalized with coreactant azobenzene molecules. The fibers bend toward a light source in a concerted manner. When placed in a liquid, the cooperative bending motion of the fibers creates a flow able to efficiently carry objects. The proposed fabrication process of the fibers is scalable to large area and requires an optimized rheology which is achieved by converting low molecular weight reactive liquid crystal acrylate monomers to oligomers using a multiplication of the monomeric units by the Michael addition reaction with dithiol. The oligomer properties and the elasticity of the fibers are adjusted by changing the thiol spacer leading to optimized manufacturing and maximized optical response.

Polarization axis-selective realignment of a photoreactive liquid crystalline composite with homogeneous alignment

We investigated the photoalignment properties of a liquid crystalline composite. The composite consisted of a low molecular weight nematic liquid crystal (LC) and a photoreactive liquid crystalline polymer containing 4-(4-methoxycinnamoyloxy)biphenyl side groups. Homogeneously aligned LC composite cells were fabricated using rubbed substrates and were then exposed to a linearly polarized (LP) ultraviolet (UV) laser beam. The alignment states of the LC composites were characterized using a LP visible laser beam. The LC composite in the cell was realigned by LP UV exposure and subsequent annealing. The direction of the realignment could be controlled by the polarization direction of the LP UV beam. The relationship between the realignment direction and the rubbing strength of the substrates was also investigated. A large realignment was induced in the LC composite cell when the azimuthal anchoring strength of the rubbed substrates was relatively weak.

Switchable photoluminescence liquid crystal coated bacterial cellulose films with conductive response

Three different low molecular weight nematic liquid crystals (LCs) were used to impregnate bacterial cellulose (BC) film. This simple fabrication pathway allows to obtain highly transparent BC based films. The coating of BC film with different liquid crystals changed transmittance spectra in ultraviolet–visible region and allows to design UVC and UVB shielding materials. Atomic force microscopy results confirmed that liquid crystals coated BC films maintain highly interconnected three-dimensional network characteristic of BC film and simultaneously, transversal cross-section scanning electron microscopy images indicated penetration of liquid crystals through the three-dimensional network of BC nanofibers. Investigated BC films maintain nematic liquid crystal properties being switchable photoluminiscence as a function of temperature during repeatable heating/cooling cycles. Conductive response of the liquid crystal coated BC films was proved by tunneling atomic force microscopy measurement. Moreover, liquid crystal coated BC films maintain thermal stability and mechanical properties of the BC film. Designed thermoresponsive materials possessed interesting optical and conductive properties opening a novel simple pathway of fabrication liquid crystal coated BC films with tuneable properties.

Thermal and optical behavior of poly(ethylene-b-ethylene oxide) block copolymer dispersed liquid crystals blends

Different block copolymer dispersed liquid crystals blends based on poly(ethylene-b-ethylene oxide) (PE-b-PEO) and modified with low molecular weight nematic liquid crystals, 4′-(hexyloxy)-4-biphenylcarbonitrile (HOBC) and N-(4-ethoxybenzylidene)-4-butylaniline (EBBA) were prepared and characterized. The miscibility between each block of PE-b-PEO block copolymer and nematic liquid crystals was studied using differential scanning calorimetry (DSC). DSC results were in good agreement with the miscibility prediction supported by the solubility parameters and miscibility effect in polymer dispersed liquid crystals blends based on polyethylene oxide (PEO) homopolymer. Thermal stability of PE-b-PEO/HOBC and PE-b-PEO/EBBA blends was also studied. Block copolymer dispersed liquid crystals blends maintained the nematic/isotropic transition in function of the ratio between PE-b-PEO block copolymer and nematic liquid crystals indicating the potential application of the designed materials.

Orienting effect of light on dye-doped liquid-crystal polymer

Light-induced reorientation of the dye-doped liquid-crystal polymer director is found and studied. The director rotates from the light field direction, which corresponds to the negative optical nonlinearity. The nonlinearity coefficient is several times larger than that of a low-molecular liquid crystal doped with the same dye.

Origin of the echo phenomenon upon flow reversal in low molecular weight nematic liquid crystals

We analyse the transient shear stress response in tumbling nematic liquid crystals upon flow reversal within the framework of Leslie–Ericksen theory. In particular, we focus our attention on the echo phenomenon, i.e. the progressive re-emergence, upon flow reversal, of the transient oscillations observed at the flow start-up in low molecular weight (LMW) liquid crystals. We show that it is possible to interpret this phenomenon if the director distribution that develops after start-up contains a reversible and an irreversible component. In short, the formation of an echo results from the reversible component while the irreversible component attenuates its amplitude. Within this model, the relative proportion of reversible and irreversible contributions to the total director distribution determines the magnitude of the echo and its rate of decay with the increasing of elapsed time between start-up and flow reversal. The model proposed in this paper is fully analytical; in particular, we give an analytical expression for the intensity of the echo. This model is in good agreement with published experimental data for the MSHMA/5CB nematic mixture (Gu et al. J Rheol 37:985–1001, 1993; Gu and Jamieson, Macromolecules 27:337–347, 1994). We end this paper with a brief discussion contrasting the reappearance of the oscillations in liquid crystal polymers and surfactants immediately after the flow reversal, with the observation of the echo phenomenon around t = 2tR in LMW liquid crystals, where tR is the time interval between the start-up and the reversal of the flow.

Effect of Field Strength on Electrooptical Properties of Low-Molecular Weight and Polymer Liquid Crystals

The influence of a strong electric field on isotropic melts of 6-cyanobiphenyl and comb-shaped polyacrylate with side mesogenic groups was investigated. It was established that the electric field induces the isotropic—nematic phase transition in melts of these compounds. A relaxation process was discovered that destroys the nematic ordering induced in substances by electric fields. It was found that the relaxation time τ of the orientational order parameter is proportional to the square of electric field strength. For comb-shaped polymer liquid crystals, the time of transition from the nematic to the isotropic phase is several orders longer then that for low-molecular liquid crystal.

Gel formation in a mixture of a block copolymer and a nematic liquid crystal

The viscoelastic properties of a binary mixture of a mesogenic side-chain block copolymer in a low molecular weight nematic liquid crystal are studied for mass concentrations ranging from the diluted regime up to a liquid crystalline gel state at about 3%. In the gel state, the system does not flow, exhibits a polydomain structure on a microscopic level, and strongly scatters light. Below the gelation point, the system is homogeneous and behaves like a usual nematic, so the continuum theory of liquid crystals can be applied for interpreting the experimental data. Using the dynamic Fréedericksz transition technique, the dependence of the splay elastic constant and the rotational viscosity on the polymer concentration have been obtained. Comparing the dynamic behavior of block copolymer solutions with the respective homopolymer solutions reveals that, above a mass concentration of 1%, self-assembling of the block copolymer chain segments in clusters occurred, resulting in a gel state at higher concentrations. The effective cluster size is estimated as a function of the concentration, and a scaling-law behavior near the sol-gel transition is confirmed. This technique may serve as an alternative method for determining the gelation point.

Conductive Properties of Photoluminescent Au/Ps-b-PEO Inorganic/Organic Hybrids Containing Nematic Liquid Crystals

Novel inorganic/organic materials based on poly(styrene-b-ethylene oxide) block copolymers (PS-b-PEO) modified with synthesized Au nanoparticles and low molecular weight liquid crystals, 4′-(hexyloxy)-4-biphenylcarbonitrile (HOBC), have been investigated. The designed materials show a good dispersion of synthesized Au nanoparticles in one block of PS-b-PEO block copolymers. The conductive properties of the designed materials were measured using tunneling atomic force microscopy (TUNA). Au nanoparticles maintain conductive properties in investigated inorganic/organic materials. Simultaneously, the addition of even small amounts of nematic HOBC liquid crystals multiplied the TUNA-current passing throughout the investigated ternary systems. Moreover, the Au-(HOBC/PS-b-PEO) systems pose photoluminescent behavior of the low molecular HOBC liquid crystals allowing the design of nanostructured multiphase materials with the conductive properties of Au nanoparticles multiplied by HOBC and the photoluminescent prop...

Orientation of Polymer Functionalized Nanorods in Thin Films

A directed self assembly of anisotropic nanostructures offers a possibility to provide unique functional materials, which are e.g., important in optoelectronic devices. We use the liquid crystalline behavior of polymer functionalized TiO2 and ZnO nanorods to apply methods well known for low molecular liquid crystals to achieve oriented thin films. Convective forces in the meniscus on a structured substrate obtain thin layers of oriented nanoparticles with a ordering parameter of S = 0.7. As another method we present the orientation of polystyrene covered ZnO nanorods under an applied electric field. The method offers a perpendicular alignment of the rods to the surface.

Phase Behavior of Mixtures of Low Molecular Weight Nematic Liquid Crystals and Photochemically Crosslinked Polyacrylates

The present work deals with theoretical and experimental studies to explore some physical properties of composite materials made of crosslinked poly(n-butylacrylate) networks and low molecular weight nematic liquid crystals (LCs). The chemically crosslinked polymers were obtained by exposure to UV radiation of initial solutions composed of a reactive monomer, n-butylacrylate, a small amount of a crosslinking agent, hexanedioldiacrylate, and a photoinitiator. To obtain different polymer network densities, the ratio of n-butylacrylate to hexanedioldiacrylate was varied prior to exposure to UV irradiation. Immersion in excess LC solvent of the obtained polymer networks allowed for the measurement of the solvent uptake by determining the size increase as function of temperature by polarized optical microscopy. A strong change of the swelling ratio was found around the nematic-isotropic transition temperatures of the two LCs involved, i.e., 4-cyano-4′-n-pentylbiphenyl known as 5CB, and the eutectic commercial mixture of cyanoparaphenylene derivatives (E7). The obtained swelling data were used to establish phase diagrams in terms of composition and temperature for three different network densities and two LCs. The phase diagrams exhibit upper criticial solution temperatures and isotropic network + nematic solvent (I + N), isotropic network + isotropic solvent (I + I), and isotropic swollen network (I) coexistence regions. The results were successfully analyzed within a theoretical model using a combination of the Flory-Rehner theory of isotropic mixing and the Maier-Saupe theory of nematic ordering.

Electro-mechanical effects in liquid crystals

Linear and quadratic electromechanical effects of liquid crystals are reviewed. Among the linear effects the piezoelectric and flexoelectric effects and their analogues in low molecular weight fluid, nematic, smectic and columnar liquid crystals, in polymeric and elastomer liquid crystals, are discussed and compared with the piezoelectricity of conventional solid piezoelectrics. As the most important quadratic electromechanical effect, an overview is given of the electrostriction effects in fluid, polymeric and rubber-like liquid-crystalline systems. These topics are rarely discussed in the liquid crystal literature, although they are becoming increasingly important for future energy conversion and micro-energy-generating devices.