Dielectric and optical properties of polymer-liquid crystal composite

Dielectric properties of polymer-liquid crystal mixture, having constituent polymer, poly-butyl methacrylate (PBMA) and liquid crystal, cholesteryl nonanoate, are reported as a function of frequency and temperature. The measurement has been done in a temperature range of 300-375 K and frequency range of 100 Hz-10 MHz. The dielectric permittivity and dielectric loss shows significant changes with the addition of polymer molecules in liquid crystal. The significant feature of composite formation is that the pure liquid crystal and polymer do not show dielectric relaxation in the frequency range covered, while the composite shows relaxation peak at a particular frequency. The optical transmittance of pure liquid crystal and composite has also been measured and compared.     

The effect of matrix composition on the electro-optical properties of polymer dispersed liquid crystal

A new type of polymer dispersed liquid crystal (PDLC) composite film has been made by polymerizing the mixture of di-methacrylates, methacrylates containing various groups and E-7. It was found that the long chain alkyl and mesogenic groups in methacrylate monomers greatly affected the saturation and threshold voltages and response time. The sharpness could be improved by addition of methacrylate monomers containing long chain alkyl and 4-butoxylbisphenyl based mesogenic group in appropriate ratios.     

Chiral molecular imprinting in liquid-crystalline network<Superscript>⋆</Superscript>

A cholesteric imprinted elastomer was obtained by cross-linking a nematic side-chain polysiloxane around a chiral template. The template was first linked to some functionalised groups of the polymer via hydrogen-bound interactions, then was removed by washing. The sample was macroscopically oriented during the synthesis; so, both a molecular chirality and a supramolecular phase chirality were topologically imprinted inside the network. Batch rebinding experiments, performed in the presence of the template or of the other enantiomer, showed that the imprinted polymer has a pronounced stereo-selectivity towards the template enantiomer. The rebinding capacity appeared to be greater than an unimprinted mesogenic network as well as than an imprinted non mesogenic one.     

Higher-order diffraction images in photorefractive materials

We report some photorefractive higher-order diffraction phenomena of a liquid crystal polymer composite. The photorefractive composite consists of the polymer poly[N-vinylcarbazole] (PVK) doped with the chromophore 4,4′-n-entylcyanobiphenyl (5CB) and the sensitizer C₆₀. In two-wave coupling experiments, the signal beam was interfered by a mutually coherent reference beam within composite materials at a small incident angle. Results are given when the composite was placed behind the focal plane, in front of the focal plane, and in the focal plane. Higher-order diffraction images were obtained by amplification and reduction. A theory of the properties of higher-order diffraction images in a photorefractive liquid crystal polymer composite is developed. The theory is in good agreement with the results of experimental work. The experiments demonstrate the feasibility of optical image processing.     

Distortion and unwinding of the helical structure in polymer-stabilized short-pitch ferroelectric liquid crystal

We report the effect of an anisotropic polymer network formed from an achiral photoreactive monomer in a short-pitch chiral SmC* phase on the distortion and the unwinding of the helical structure of the ferroelectric phase. The electro-optical behaviour and ferroelectric properties were experimentally determined for films containing various polymer concentrations. The critical field, E_u, for the transition from the distorted structure to the homogeneous state was measured as a function of polymer concentration. A linear increase of E_u versus polymer concentration was observed, showing that the helical structure of the short-pitch SmC* phase was stabilized by the polymer network. This behaviour was expected to be a consequence of the increase of the apparent elastic constants of the ferroelectric liquid crystal stabilized by the anisotropic polymer network films. The polymer network morphology was investigated using atomic-force microscopy, revealing a twisted structure of the polymer fibers. This twisted structure was transferred onto a polymer network during the polymerization process within a short-pitch SmC* phase. The increase of the apparent elasticity can then be interpreted by a strong interaction between polymer network and the liquid-crystal molecules. From our experimental data, the coupling coefficient, W_p, characterizing this interaction was evaluated for all studied polymer concentrations.     

Linear and non-linear dielectric properties of a short-pitch ferroelectric liquid crystal stabilized by a polymer network

Linear and non-linear dielectric measurements were carried out on a ferroelectric liquid crystal stabilized by an anisotropic polymer network. The polymerization process was achieved at room temperature. It was performed from an achiral monomer in the ferroelectric chiral smectic C phase, exhibiting a very short helical pitch and a large polarization. The linear and non-linear dielectric spectroscopy were also completed by textural morphology as well as structural and ferroelectric characterizations. All these measurements were carried out on a pure ferroelectric liquid crystal material and on composite films containing two polymer concentrations. The increase of the polymer network density leads to a decrease of the dielectric strength determined in the linear and non-linear dielectric spectroscopy. The complementarity between the linear and non-linear dielectric measurements and their confrontation with a theoretical model allowed the simultaneous determination of some physical parameters such as macroscopic polarization, rotational viscosity and twist elastic energy. We also discuss the effect of the polymer network density on the obtained physical parameters.     

Novel properties of nanoscale organic–inorganic systems and photonic crystals — conducting polymers in nanoscale periodic structures,microcavities and photonic crystals

Conducting polymer/C₆₀and C₆₀doped conducting polymer/C₆₀heterojunctions have been fabricated and found to exhibit remarkably enhanced photoresponse due to the highly effective photoinduced charge transfer at the interface. In conducting polymer/C₆₀alkali metal nanoscale composite systems, multiphase superconductivity has been clarified and explained by taking the coupling of nanoscale grains by Josephson junctions into consideration. As examples of intramolecular organic-inorganic combined systems, unique electrical and optical characteristics have been revealed in oligosilanylene oligophenylene polymers. Electroluminescence has been demonstrated in organic-inorganic junction devices such as conducting polymer/porous Si and conducting polymer/diamond junctions. Conducting, polymer-based nanoscale multilayer systems have been studied utilizing molecular self-assembly method and novel photosensitive characteristics have been revealed. \indent Novel optical and electrical properties of conducting polymers infiltrated in a photonic crystal, synthetic opal made of SiO₂spheres of several hundred nm in diameter, and also a conducting polymer replica have been revealed. A clear diffraction pattern was observed in a photonic crystal infiltrated with conducting polymers, and transmission spectra are dependent on various ambient conditions. Their photoluminescence (PL) spectra, spectral narrowing of PL and lasing characteristics at relatively low optical excitation have also been clarified. Novel conducting characteristics of conducting polymers in a photonic crystal that was prepared by pyrolysis of a polymer replica of opal have also been observed.     

Freedericksz transition in polymer-stabilized nematic liquid crystals

We have constructed polymer-stabilized nematic liquid crystals by photopolymerizing diacrylate monomers in the nematic phase. The orientation of the liquid crystal was controlled by the polymer network. We studied the Freedericksz transition in these systems. Experimentally we studied the transition by measuring the capacitance of the liquid crystal cells as a function of applied voltage. The transition was affected profoundly by the dispersed polymer network. The threshold was higher with shorter interpolymer network distance. Theoretically we studied the systems using a two-dimensional model in which the polymer networks were represented by parallel cylinders with random location. The interaction between the liquid crystal and the polymer network was described by the boundary condition imposed by the polymer network. By fitting the experimental data, we found that the polymer cylinders had diameters of a few submicrons, and a substantial amount of liquid crystal was trapped inside the cylinders.     

A free-standing and thermostable polymer/plastic crystal electrolyte for all-solid-state lithium batteries

All-solid-state lithium batteries using flexible solid electrolytes instead of combustible organic liquid electrolytes are the ultimate solution to address the safety problem of commercialized lithium ion batteries. In this study, a free-standing and thermostable polymer/plastic crystal composite electrolyte (PPCE) based on polymerized trimethylolpropane trimethacrylate (TMPTMA)-1, 6-hexanediol diacrylate (HDDA) matrix, and plastic crystal electrolyte was prepared for all-solid-state lithium batteries. The polymerized TMPTMA-HDDA-based matrix of a porous network structure coupled with plastic crystal electrolyte (PCE) in the pores reveals good compatibility. The as-synthesized PPCE possesses excellent flexible performance, thermostability, and high conductivity, showing that PPCE can reach 8.53 × 10^?4 S cm^?1 with 7.5 wt% monomers (PPCE-7.5%) at 25 °C under a stability electrochemical window above 5.2 V. The assembled lithium batteries Li|PPCE|LiFePO₄ exhibit high capacity and highly cycling stability at room temperature, indicating great potential of all-solid-state lithium batteries.     

Structural and dielectric properties of polyvinyl alcohol/barium zirconium titanate polymer–ceramic composite

The polyvinyl alcohol (PVA)/barium zirconium titanate Ba[Zr_0.1Ti_0.9]O₃ (BZT) polymer–ceramic composites with different volume percentage are obtained from solution mixing and hot-pressing method. Their structural and electrical properties are characterized by X-ray diffraction (XRD), Rietveld refinement, cluster modeling, scanning electron microscope and dielectric study. XRD patterns of PVA/BZT polymer–ceramics composite (with 50% volume fractions) indicate no obvious differences than the XRD patterns of pure BZT which shows that the crystal structure is still stable in the composite. The scanning electron micrograph indicates that the BZT ceramic is dispersed homogeneously in the polymer matrix without agglomeration. The dielectric permittivity (ε_r) and the dielectric loss (tan δ) of the composites increase with the increase of the volume fraction of BZT ceramic. Theoretical models are employed to rationalize the dielectric behavior of the polymer composites. The dielectric properties of the composites display good stability within a wide range of temperature and frequency. The excellent dielectric properties of these polymer–ceramic composites indicate that the BZT/PVA composites can be a candidate for embedded capacitors.     

Characteristics of color optical shutter with dye-doped polymer network liquid crystal

The optical properties and the theoretical prediction of color optical shutter with dye-doped polymer network liquid crystal (PNLC) were investigated. The view-angle dependence of reflectance according to the bias conditions showed distinctive characteristics, which could be explained from the effects of dye absorption and path length. It was also shown that the thickness dependence of reflectance was strongly influenced by the light-scattering coefficient. Our experimental results matched up well with the theoretical prediction based on the light scattering of liquid crystals in polymer network and the absorption of dichroic dye. This work indicates potential to improve the optical device using dye-doped liquid crystal-polymer composite.     

Improving electret properties of PP filaments with barium titanate

Barium titanate (BaTiO₃) containing polypropylene (PP) composite filaments were melt spun to modify polymer electrostatic charging characteristics. Sample filaments were charged with a corona instrument and their surface potentials were measured. Initial surface potential as well as potential stability was monitored through an accelerated decay procedure. It was found that both BaTiO₃ concentration and charging temperature influence the charging characteristics of the fibers. When BaTiO₃/PP composite filaments were charged at 130 °C, significant enhancements were observed when compared to samples charged at room temperature. The distribution of BaTiO₃ particles within the filaments and changes in the crystal structure were also examined.     

Influence of K<Subscript>2</Subscript>Ti<Subscript>6</Subscript>O<Subscript>13</Subscript> on dielectric and barrier properties of polymer

Polymer composite comprising polyvinylidene fluoride (PVDF) and potassium hexatitante (K₂Ti₆O₁₃) was synthesized by solution casting. The effect of K₂Ti₆O₁₃ on surface, thermal, and electrical properties of polymer composite were investigated. The addition of K₂Ti₆O₁₃ with polymer leads to thermal degradation and transition of polymer composite from semi-crystalline to amorphous phase. The optimum results of contact angle for different loading wt% of K₂Ti₆O₁₃ were directly correlated with the surface morphology. Our experimental results confirmed the incorporation of K₂Ti₆O₁₃ in polymer by SEM micrographs. The evaluated dielectric properties (ε' = 424; tan δ = 2.14 at 130 °C and 100 Hz frequency for 20 wt% loading of K₂Ti₆O₁₃) for polymer composite are higher in compared to pure polymer. The enhancement in dielectric constant and changing the surface properties of polymer composite can be used for the development of electrochemical storage device applications.     

New fabrication method for anisotropic gratings formed in photocrosslinkable polymer liquid crystals

We present a new fabrication method, called two-step ultraviolet exposure, to prepare anisotropic gratings in photocrosslinkable polymer liquid crystal films. Using the controllability of the reorientation direction of mesogenic molecules, anisotropic phase gratings, in which the mesogenic molecules were periodically modulated in orthogonal directions, were prepared by the use of one grating photomask. The resultant gratings diffract the light and convert the polarization states at the same time, and have applications as diffraction optical devices. PACS 42.65.Hw; 42.70.Df; 42.70.Nq; 78.20.-e; 78.40.Me     

Influence of solid electrolyte particles size on ionic transport in model composite system (PVdF-HFP–Li1.3Al0.3Ti1.7(PO4)3)

The influence of filler particles size on lithium ion conductivity of composite polymer electrolytes was issued on model system vinylidenefluoride with hexafluoropropylene (PVdF-HFP)–Li_1.3Al_0.3Ti_1.7(PO₄)₃. Model electrolyte objects with filler grains of different sizes were prepared using a modified solvent casting method from a mixture of PVdF-HFP solution in dimethylformamide and Li_1.3Al_0.3Ti_1.7(PO₄)₃ solid electrolyte particles. The percolation threshold was defined and the transport properties of composite polymer electrolytes at different volume concentrations of the solid electrolyte investigated. A significant decrease in conductivity compared to that of ceramic solid electrolytes was observed. The size of the filler particles was found to affect the structure and transport properties of the prepared composite polymer electrolytes. The conductivity of the composite polymer electrolyte at 100 °C was found to increase by two orders of magnitude with the tenfold increase of the size of the filler particles.     

Structure and frustration in liquid crystalline polyacrylates I. Bulk behaviour

The phase behaviour and structure are reported of a new type of frustrated side-chain liquid crystalline (LC) polymer, a polyacrylate with phenylbenzoate mesogenic side groups and a narrow polydispersity. At a high degree of polymerisation the LC polymers show a nematic, a smectic-A_d, a re-entrant nematic and a C phase, for shorter chains only a nematic and a C phase. This constitutes a new example of nematic re-entrance for which the driving field is the length of the polymer chain. The smectic-A_d layers consist of partially overlapped side groups while in the C phase the side chains are rearranged into chevron-like blocks of bilayers. We propose an explanation of the frustrated phase behaviour in terms of these two different competing length scales and their coupling to the backbone conformations. Received 28 February 2001 and Received in final form 6 August 2001     

Molecular dynamics simulations of a flexible liquid crystal

Molecular dynamics simulations have been performed for a liquid crystal composed of a Gay—Berne core site with two alkyl chains of different length (C₇ and C₃) at either end of the molecule. Calculations have been carried out for 512 molecules in the NVT ensemble for simulation times of up to 8.0ns at two distinct densities. The liquid crystal phases of the material have been fully characterized by measurements of orientational order parameters and radial distribution functions in each phase. Results are also presented for conformational distributions and effective torsional potentials of the system. We conclude that models of this nature represent a powerful approach to the study of flexibility in mesogenic systems and open up possibilities for predicting both the phase behaviour and bulk properties of liquid crystals based solely on a prior knowledge of intermolecular interactions.     

Electrically induced storage effects in smectic A phase of dyed low molar mass siloxane liquid crystals

A newly synthesized low molar mass liquid crystal having a flexible mesogenic group attached to methylene siloxane exhibiting smectic A phase has been used as a host for 2% (wt./wt.) dichroic dyes. The electro-optic properties of these guest–host mixtures have been studied as a function of temperature, frequency and the applied voltage. At low frequency (≲1 Hz), turbulent scattering texture was induced influenced by conduction mechanism. This texture was transformed to a clear homeotropic state due to dielectric reorientation of the smectic molecules at high frequency (>2 kHz). These materials have shown storage effects similar to monomeric and polymer smectogens. The effects of dichroic dyes on the electro-optic performances have been discussed. These systems are expected to prove functional materials for electronic displays.     

Orientational structure transformations caused by the electric-field-induced ionic modification of the interface in nematic droplets

The films of a polymer-dispersed nematic liquid crystal doped with an ionic surfactant were studied. The surface-anchoring modification effect caused by the local increase in the concentration of surface-active ions was observed at the polymer-liquid crystal interface under the action of an electric field. The modification of the boundary conditions leads to the transformation of the orientational structure of the nematic droplets and, as a result, to an appreciable change in their texture patterns and light-scattering efficiency at the interfaces. The monopolar director configurations (normal and curved) arising in the process of orientational structure transformations are considered and their typical textures are demonstrated. The possibility that the monopolar structure can be formed is theoretically substantiated by the computer simulation of the director field in a nematic droplet with the boundary conditions corresponding to the experiment.     

Improved Dielectric Breakdown Strength of Covalently-Bonded Interface Polymer–Particle Nanocomposites

Interfacial covalent bonding is an effective approach to increase the electrical resistance of a polymer–particle composite to charge flow and dielectric breakdown. A bifunctional tether reagent bonded to an inorganic oxide particle surface assists with particle dispersion within a thermosetting epoxy polymer matrix but then also reacts covalently with the polymer matrix. Bonding the particle surface to the polymer matrix resulted in a composite that maintained the pure polymer glass transition temperature, compared to modified or unmodified particle dispersions that lacked covalent bonding to the polymer matrix, which depressed the polymer glass transition to lower temperatures. The added interfacial control, directly bonding the particle to the polymer matrix, appears to prevent conductive percolation across particle surfaces that results in a reduced Maxwell–Wagner relaxation of the polymer–particle composite and a reduced sensitivity to a dielectric breakdown event. The inclusion of 5 vol% particles of higher permittivity produces a composite of enhanced dielectric constant and, with surface modification to permit surface cross-linking into the polymer, a polymer–particle composite with a Weibull E ₀ dielectric breakdown strength of 25% greater than that of the pure polymer resulted. The estimated energy density for the cross-linked interface composite was improved 260% compared to the polymer alone, 560% better than a polymer–particle composite synthesized using bare particles, and 80% better than a polymer–particle composite utilizing bare particles with a dispersant.