Reverse-mode polymer dispersed liquid crystal films prepared by patterned polymer walls

This article proposes a methodology to prepare polymer dispersed liquid crystal (PDLC) films working in the reverse-mode operation, where the ion-doped nematic liquid crystals (NLCs) with negative dielectric anisotropy (Δε) were locked by polymer walls. On-state and off-state of films were controlled by an electric field. In the absence of an electric field, it appears to be transparent. In the field, the homogeneous alignment NLCs form dynamic scattering, giving rise to opaque. The effect of the cylindrical holes with different diameters of photo masks and liquid crystal Δε on the electro-optical properties and transmittance wavelength range of 400–3000 nm light of samples were investigated. It was found that it exhibited very good electro-optical characteristics, high contrast ratio and excellent infrared energy-efficient of films used as switchable windows.     

Nano P(VDF-TrFE) doped polyimide alignment layers for twisted nematic liquid crystal devices

ABSTRACT

The rapid development of consumer electronics and portable devices imposes a great demand for energy efficient information display systems. Among the information display devices, liquid crystal display (LCD) devices stands in the front. The fabrication of energy-efficient LCD systems demands new material and techniques. In this work, the conventional polyimide alignment layer of twisted nematic liquid crystal device (TNLCD) was replaced with ferroelectric polymer nanoparticle doped alignment layer. Morphology of the alignment layer was analysed using field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The ferroelectric nature of the polymer alignment layer was studied using dynamic contact electrostatic force microscopy (DC-EFM). TNLCD cells are fabricated with this modified alignment layer and the switching characteristics are compared with the conventional TNLCD devices. The TNLCD with modified alignment layer has shown a reduction of 50% in threshold (V_thr) and 47% reduction in saturation voltage (V_sat).     

The role of segregation in the polarized emission from polyfluorene embedded in a liquid crystal

Polyfluorene (PFO) embedded in a nematic liquid crystal (LC) matrix is investigated. For low PFO weight contents, a homogeneous dispersion is obtained which displays a strong fluorescence anisotropy along the LC director, indicating a significant alignment of the polymeric chains along this direction. Besides, for relatively high PFO weight contents, phase separation takes place. Under these conditions, the sample is composed of micrometer‐sized domains, where the two species are in solution, enclosed by segregated polymeric boundaries. By polarized‐photoluminescence imaging and spectroscopy, it is found that most of the light emission originates from these boundaries and gets strongly pinned along their orientation. Since boundaries are mainly oriented orthogonal to the LC chains, this morphological alignment results in a system in which the orientation of the polarization emission can be predicted and possibly controlled. Conversely, in the homogeneous sample one can obtain a homogeneous emission polarization by controlling the alignment of the LC. These features are potentially relevant for the development of flexible polarization‐sensitive optoelectronic devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1558–1563     

Shape recovery liquid crystal elastomer synthesized by melt‐polycondensation

A novel liquid crystal elastomer (LCE) synthesized by melt polymerization, which exhibits the capacity of shape memory, is reported here for the first time. The method of synthesize the shape memory LCE has been explored. A facile two‐step method to synthesize these anisotropic materials to realize reversible shape change behavior is reported. The first reaction is the addition of nematic liquid crystal molecules to form a kind of liquid crystal polymer. Subsequently, the polymer is crosslinked to trap the order of the liquid crystal into a crosslinked LCE. The LCE exhibits liquid crystalline behavior which has shape memory with excellent fixity and recovery. Its shape memory and actuating properties also have been studied. When reheating the LCE to 165 °C, the shape will recover. The main chains and crosslinked bonds of the LCE contain ester groups, which are sensitive to alkaline and acidic condition. It turns out that the LCE is intact under acidic condition, but it can be degraded under alkaline condition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 389–394     

Nematic–isotropic phase behaviors of polydisperse polymer/liquid‐crystal systems: Chain‐length‐dependent interaction parameter

Phase behaviors of polydisperse polystyrene (PS)/nematic liquid‐crystal systems [P‐ethoxy ‐ benzylidene ‐ p ‐ n‐butylaniline (EBBA)] are investigated with a thermo‐optical analysis technique. We also develop a thermodynamic framework to describe the phase behaviors of polydisperse PS/EBBA systems. The proposed model is based on a modified double‐lattice model to describe isotropic mixing and Maier–Saupe theory for anisotropic ordering. To correlate the polymer chain length and energy parameters in a nematic–isotropic biphasic region and to apply the primary interaction parameter in an isotropic–isotropic phase‐transition behaviors of polydisperse PS/EBBA systems. The proposed model shows remarkable agreement with experimental data for the model systems in comparison with an existing model. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1031–1039, 2006     

Structure—Property relationships for exciton transfer in conjugated polymers

The ability of conjugated polymers to function as electronic materials is dependent on the efficient transport of excitons along the polymer chain. Generally, the photophysics of the chromophore monomer dictate the excited state behavior of the corresponding conjugated polymers. Different molecular structures are examined to study the role of excited state lifetimes and molecular conformations on energy transfer. The incorporation of rigid, three‐dimensional scaffolds, such as iptycenes and cyclophanes, can encourage an oblique packing of the chromophore units of a conjugated polymer, thus allowing the formation of electronically‐coupled aggregates that retain high quantum yields of emission. Rigid iptycene scaffolds also act as excellent structural directors that encourage complete solvation of PPEs in a liquid crystal (LC) solvent. LC‐PPE mixtures display both an enhanced conformational alignment of polymer chains and extended effective conjugation lengths relative to isotropic solutions, which leads to enhanced energy transfer. Facile exciton migration in poly(p‐phenylene ethynylene)s (PPEs) allows energy absorbed over large areas to be funneled into traps created by the binding of analytes, resulting in signal amplification in sensory devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Effect of crosslinking polymer networks on the molecular reorientation and electro‐optical performance of in‐plane switching vertically aligned liquid crystal devices

The effects of crosslinking polymer networks (PNs) on the molecular reorientation and electro‐optical properties of vertically aligned (VA) liquid crystal (LC) devices are investigated by applying an in‐plane switching (IPS) electric field. Through the polymerization process, crosslinking PNs are developed on the substrate surface, effectively increasing the anchoring energy and governing the LC molecular reorientation. With its stronger anchoring effect, the PNs cell shows good light transmittance and excellent vertical alignment quality, as compared to the pure LC cell. Furthermore, the alignment transformation and transmittance bounce resulting from the transient process of LC molecular reorientation are eliminated when the cell is operated at high voltages. The rising‐time (t_r) and falling‐time (t_f) responses of the PNs cell are significantly improved, and around 36% improvement in the optical switching response is obtained. In addition, the dynamic gray‐level t_r and t_f responses of the PNs cell are enhanced by around 55% and 42%, respectively, at a low driving voltage (～12 V). This developed VA‐IPS LC/PNs cell benefits not only the LC molecular alignment but also the electro‐optical performance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1123–1130     

A switchable optical diffuser based on a polymer/nematic liquid crystal composite film with transient polymer balls-networks microstructure

ABSTRACT

With the increasing development of multifunction liquid crystal displays (LCDs), multifunction optical diffusers have attracted more attention. In this work, switchable optical diffusers based on the transient polymer balls-networks in polymer/nematic liquid crystal composite films have been prepared and investigated, and the effects of thiol content, curing time, LC content and photo-initiator content on the polymer microstructures and optical properties of optical diffusers are systematically studied. An optical diffuser with the transient polymer balls-networks microstructure has achieved the high transmission (96.42%), high haze (90.49%), excellent optical diffusing ability and wide viewing angle of 150° (from ?75° to 75°) on its off state. By the application of electric field of 40.0 voltage, the viewing angle of the optical diffuser turns to be narrower (from ?60° to 60°), which gives great applications in tunable viewing angle devices and other electric optical devices.     

Controllable alignment of nematics by nanostructured polymeric layers

A method for a continuous control of the pretilt angle of the easy axis in the range 0–90° degrees and of the anchoring strength by using nanostructured polymers as alignment layers is described. The nanostructured polymers are blends of two different side-chain polymers each of them promoting planar and homeotropic alignment, respectively. A model to interpret the alignment of a nematic liquid crystal induced by such polymer layers is proposed. We show that in this case the anisotropic part of the surface tension can be approximated by a simple extension of the Rapini–Papoular expression. The predicted trend of the pretilt of the easy axis versus the concentration of the side-chain polymer promoting the planar alignment, for instance, is in good agreement with the experimental data. We also show that the effective anchoring strength of the system depends on the concentration of the side-chain polymer promoting planar alignment, and exhibits a minimum for a well-defined value of this quantity. The results obtained in this work seems to be of importance for liquid crystal displays technology since the control of the pretilt and the anchoring strength strongly affect the performance of liquid crystal displays.     

High‐molecular‐weight side‐chain liquid‐crystalline polyethers based on 4′‐cyanobiphenyl‐4‐oxy mesogenic groups

A set of poly[ω‐(4′‐cyano‐4‐biphenyloxy)alkyl‐1‐glycidylether]s were synthesized by the chemical modification of the corresponding poly(ω‐bromoalkyl‐1‐glycidylether)s with the sodium salt of 4‐cyano‐4′‐hydroxybiphenyl. New high‐molecular‐weight side‐chain liquid‐crystalline polymers were obtained with excellent yield and almost quantitative degree of modification. All side‐chain liquid‐crystalline polymers were rubbers soluble in tetrahydrofuran. The characterization by ¹H and ¹³C NMR revealed no changes in the regioregular isotactic microstructure of the starting polymer and the absence of undesirable side reactions such as deshydrobromination. The liquid crystalline behavior was analyzed by DSC and polarized optical microscopy, and mesophase assignments were confirmed by X‐ray diffraction. Polymers that had alkyl spacers with n = 2 and 4 were nematic, those that had spacers with n = 6 and 8 were nematic cybotactic, and those that had longer spacers (n = 10 and 12) were smectic C and showed some crystallization of the side alkyl chains. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3002–3012, 2004     

Preparation of Poly(3,4‐ethylenedioxythiophene) in a Chiral Nematic Liquid‐Crystal Field

Summary: The 3,4‐ethylenedioxythiophene (EDOT) monomer in a chiral nematic liquid‐crystal electrolyte was polymerized by application of a voltage to yield a thin film. Circular dichroism measurements indicated a Cotton effect for the film. Optical texture suggests that the polymer shows a finger‐print texture and a spiral texture similar to that of the chiral nematic phase. This simple method provides a new technique for preparing chiral conducting films in a thermotropic chiral liquid‐crystal field.

Optical micrograph of (R)‐PEDOT* (no polarizer).     

Liquid crystalline conjugated polymers and their applications in organic electronics

This article describes the syntheses and electro‐optical applications of liquid crystalline (LC) conjugated polymers, for example, poly(p‐phenylenevinylene), polyfluorene, polythiophene, and other conjugated polymers. The polymerization involves several mechanisms: the Gilch route, Heck coupling, or Knoevenagel condensation for poly(p‐phenylenevinylene)s, the Suzuki‐ or Yamamoto‐coupling reaction for polyfluorenes, and miscellaneous coupling reactions for other conjugated polymers. These LC conjugated polymers are classified into two types: conjugated main chain polymers with long alkyl side chains, namely main‐chain type LC polymers, and conjugated polymers grafting with mesogenic side groups, namely side‐chain type LC conjugated polymers. In general, the former shows higher transition temperature and only nematic phase; the latter possesses lower transition temperature and more mesophases, for example, smectic and nematic phases, depending on the structure of mesogenic side chains. The fully conjugated main chain promises them as good candidates for polarized electroluminescent or field‐effect devices. The polarized emission can be obtained by surface rubbing or thermal annealing in liquid crystalline phase, with maximum dichroic ratio more than 20. In addition, conjugated oligomers with LC properties are also included and discussed in this article. Several oligo‐fluorene derivatives show outstanding polarized emission properties and potential use in LCD backlight application. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2713–2733, 2009     

Spontaneous formation of hierarchical proton‐conductive structures in sulfonated poly(p‐phenylene terephthalamide) copolymer films

Two partially sulfonated copolymers of poly(p‐phenylene terephthalamide) were studied; the sulfonated diamine to nonsulfonated diamine ratios were x = 1 and x = 2. Polymer solutions in water demonstrated lyotropic liquid‐crystalline behavior, with the critical concentration for nematic phase formation being around 0.7 wt %. Films of these copolymers could be considered for fuel‐cell applications. The in‐plane proton conductivities were of the order of 10^?3 to 10^?2 S cm^?1 between 20 and 90 °C. Increasing the sulfonation level resulted in a more conductive material. Spontaneous alignment of the polymer occurred during film formation, as revealed by X‐ray diffraction. Scattering along the polymer backbone was observed perpendicular to the film, implying that the polymer chains were homeotropically aligned with respect to the film. The average degree of alignment was determined to be 0.66 and 0.77 for x = 1 and x = 2, respectively. Evidence of secondary layering within the plane of the film was seen in SEM images. These layers could provide a pathway for proton conduction to occur within the plane of the film. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 666–676, 2007     

Temperature induced structural evolution of a fluorene‐thiophene copolymer on rubbed surfaces

The thermal alignment of the liquid crystalline fluorene‐thiophene copolymer (F8T2) on rubbed polyimide surfaces is investigated by ex‐situ and in‐situ X‐ray scattering experiments. The ex‐situ characterization allows an assignment of the observed diffraction peaks to distances between polymer backbones (1.6 nm), distances between the flexible side groups of the polymer chains (0.43 nm), and intramolecular distances of adjacent ring units (0.5 nm). The in‐situ characterization allows a temperature dependent observation of the polymer chain alignment. A gradual alignment process of the polymer backbones is observed for temperatures up to 563 K. Decreasing temperature after the polymer chain alignment is accompanied by a glass transition of the side chains at 380 K. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47:1599–1604, 2009     

Mesophase transition-induced reorientation in a stretched side-chain liquid crystalline polymer

The orientation relaxation behavior of a stretched side-chain liquid crystalline polymer (SCLCP) on a poly(vinyl alcohol) (PVA) film under strain was investigated through infrared dichroism at temperatures near its phase transitions. We found a reorientation of the aligned mesogens over the smectic to nematic transition of the SCLCP, changing the alignment from an initially, mechanically induced perpendicular orientation to a parallel orientation with respect to the film-stretching direction. This reorientation was found to be irreversible during subsequent nematic to smectic transition, with the parallel orientation preserved. We show that it is possible to stop the reorientation process by cooling the SCLCP back to its smectic phase just before the change in the alignment direction. Moreover, this interruption can result in a stable, zero macroscopic orientation of the mesogens in the stretched SCLCP, and a subsequent heating to the smectic-nematic transition allows the reorientation process to restart and to be completed. We discuss the possible mechanisms for this mesophase transition-induced reorientation and the factors that could influence the process. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1491–1499, 1997     

Ultrafast switchable wide angle negative refraction in novel dual-frequency liquid crystal mixture

Ultrafast switchable wide angle negative refraction in a novel dual-frequency liquid crystal mixture is demonstrated experimentally. Laterally fluorinated isothiocyanato phenyl-tolane liquid crystal compound is doped into Merck MLC-2048 to acquire the high birefringence dual-frequency liquid crystal. The maximum negative refraction angle achieved is about 12° and the switching time is only 25 ms for a 40-μm cell which is two orders faster than switchable negative refraction achieved before in nematic liquid crystals. Such properties provide a feasible approach to design negative refraction devices based on liquid crystals.     

Light‐Driven Reversible Alignment Switching of Liquid Crystals Enabled by Azo Thiol Grafted Gold Nanoparticles

Stimuli‐directed alignment control of liquid crystals (LCs) with desired molecular orientation is currently in the limelight for the development of smart functional materials and devices. Here, photoresponsive azo thiol (AzoSH) was grafted onto gold nanoparticles (GNPs). The resulting hybrid GNPs were able to homogeneously mix with a commercially available nematic LC host, as evidenced by Cryo‐TEM. Interestingly, the LC nanocomposites were found to undergo reversible alignment transition upon light irradiation as a consequence of the trans–cis photoisomerization of the azo groups on the GNP surface. LC molecules in either planar or bare glass cells were able to change their alignment to vertical upon UV irradiation, while the vertically aligned LC molecules returned to the planar or random orientation under visible irradiation. Neither the azo thiol molecules nor the unfunctionalized GNPs alone promoted the alignment of the LC molecules in the system upon light irradiation. The photoinduced vertical alignment without applied electric or magnetic field was very stable over time and with respect to temperature. Furthermore, an optically switchable device based on the photostimulated reversible alignment control of LCs was demonstrated.     

Response of a biphasic poly(n‐hexyl isocyanate)/p‐xylene solution to applied high electric fields

The effect of a high electric field on a solution of a lyotropic liquid‐crystalline polymer, poly(n‐hexyl isocyanate) in p‐xylene, was studied. The application of a high‐voltage alternating‐current electric field to the biphasic solution resulted in an elongation of the nematic domains in the field direction, the degree of elongation varying approximately with the square of the electric field. At a constant field, the extent of elongation decreased, varying inversely with the frequency in an exponential fashion. The domain structure and thus the molecular orientation were examined to explain these electric field effects. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1124–1133, 2005     

Short wavelength light reflecting films from side‐chain liquid crystal homopolymers with chiral spacers

A series of acrylate monomers with alkoxy tails of varying lengths are synthesised and polymerised. The butoxy analogue had a stable enantiotropic cholesteric liquid crystalline phase which formed a grandjean texture when prepared as a thin film between glass slides. The polymer was mixed with a low molar mass nematic liquid crystal in various proportions and the pitch of the chiral nematic phases were determined using a cano‐wedge cell technique. The polymer prepared from (S)‐2‐(4‐butoxyphenyl‐4′‐benzoyloxy)‐1‐methyl ethyl acrylate had a pitch length of 113 nm which indicates that the polymer film could be employed in optical devices requiring selective reflection of light with short wavelengths in the region of 170 nm. Copyright © 2001 John Wiley & Sons, Ltd.     

A sub-hertz frequency dielectric relaxation process in a ferroelectric liquid crystal material

Dielectric studies of the first order phase transition of a ferroelectric liquid crystal material having the phase sequence chiral nematic to smectic C* have been performed using thin (2.5 mum) cells in the frequency range 0.01 Hz to 12 MHz. For planar alignment, one of the cell electrodes was covered with a polymer and rubbed. Optically well defined alignment was obtained by applying an a.c. field below the N*-SmC* transition. Charge accumulation was enhanced by depositing a thick polymer aligning layer for the alignment of the liquid crystal molecules. A sub-hertz frequency dielectric relaxation process is detected in smectic C*, in the chiral nematic and a few degrees into the isotropic phase, due to the charge accumulation between the polymer layer and the ferroelectric liquid crystal material. The effect of temperature and bias field dependences on the sub-hertz dielectric relaxation process are reported and discussed.