Orientation and anchoring effects in stretched polymer dispersed nematic liquid crystals

The induction of liquid crystal orientation through mechanical stretching was investigated for polymer dispersed liquid crystals (PDLCs) by means of infrared dichroism. Using a nematic liquid crystal BL006 and polyacrylic acid as the polymer matrix, it was possible to stretch the PDLC films with BL006 in either the isotropic or the nematic phase. After cooling the films under strain to room temperature, the molecular orientation of BL006 was found to be much higher for films that contained isotropic liquid droplets of BL006 at the time of stretching than for films that had nematic droplets. Stretching PDLC films with isotropic droplets results in no molecular orientation, but the orientation is induced during the subsequent cooling when BL006 goes through the isotropic-to-nematic phase transition. Interestingly for PAA/BL006, the nematic director orients along the long axes of the elongated droplets despite liquid crystal anchoring perpendicular to the polymer interface.     

Optical properties of stretched polymer dispersed liquid crystal films

The basic mechanisms determining the formation of optical anisotropy in stretched, thin polymer dispersed liquid crystal (PDLC) films with micron sized nematic droplets have been studied experimentally and the results analysed in terms of a proposed theoretical model. The experiments were performed on PDLC films with the bipolar nematic director configuration in the droplets, where the film transmittance, microscopic structure, and birefringence of the polymer matrix were studied. It is shown that the orientational ordering of bipolar nematic droplets, introducing the main contribution to the ability of stretched PDLC film to polarize the transmitted light, is strongly dependent upon initial droplet shape and the elastic properties of the polymer matrix. The 'anomalous' nematic director orientation is also observed in a portion of elongated droplets where the axes of bipolar configurations do not coincide with the major axes of the droplet cavities due to the presence of inclusions at the cavity walls. The effect of alternation of droplet size and shape upon stretching and the influence of optical anisotropy of the polymer matrix on film transmittance are analysed. On the basis of the results obtained, simple criteria for optimization of main PDLC polarizer performance are formulated.     

Oriented polymer dispersed discotic liquid crystals

Polymer dispersed discotic liquid crystals (PDDLCs) were prepared using the hexa-n-octanoate of rufigallol (RHO) and three polymer matrices: polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA). The molecular orientation of RHO in stretched PDDLC films was characterized by means of infrared dichroism. It was found that the stretching of films that contain RHO in both the columnar D1 and crystalline phase can effectively align columns of RHO along the stretching direction, with the short axes of the rigid cores lying in the plane of the film. By contrast with stretched polymer dispersed nematic liquid crystals, no orientation of RHO is induced for films stretched with RHO in the isotropic phase, followed by rapid cooling to room temperature. However, if stretched films are cooled under strain into the columnar D1 phase, orientation of RHO can develop with time.     

Oriented polymer dispersed discotic liquid crystals

Polymer dispersed discotic liquid crystals (PDDLCs) were prepared using the hexa-n-octanoate of rufigallol (RHO) and three polymer matrices: polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA). The molecular orientation of RHO in stretched PDDLC films was characterized by means of infrared dichroism. It was found that the stretching of films that contain RHO in both the columnar D1 and crystalline phase can effectively align columns of RHO along the stretching direction, with the short axes of the rigid cores lying in the plane of the film. By contrast with stretched polymer dispersed nematic liquid crystals, no orientation of RHO is induced for films stretched with RHO in the isotropic phase, followed by rapid cooling to room temperature. However, if stretched films are cooled under strain into the columnar D1 phase, orientation of RHO can develop with time.     

The relationship between formation kinetics and microdroplet size of epoxy-based polymer-dispersed liquid crystals

Polymer films containing dispersions of liquid crystal microdroplets have considerable potential for use in displays and other light control devices. These polymer-dispersed liquid crystal (PDLC) films operate by electric field control of light scattering, rather than by polarization control as in the case of twisted nematic systems. The scattering characteristics of the PDLC films are determined by the refractive indices of the polymer and liquid crystal and by the size of the microdroplets. We have found that it is possible to regulate the microdroplet size by controlling the droplet formation rate (i.e. the cure kinetics of the film). Using calorimetry and scanning electron microscopy, we determined the influence of cure kinetics on microdroplet size for epoxy-based PDLCs. We found that droplet size increased with increasing cure time constant. However, the relationship changed as cure temperature was varied, perhaps as a result of competing cure processes. We also determined the phase behaviour of the epoxy-based PDLCs. The liquid crystal acted as a plasticizer, depressing the glass transition temperature of the PDLC samples slightly below that of the pure epoxy. The temperature and enthalpy of the nematic to isotropic transition of the liquid crystal material in the microdroplets were both functions of cure temperature. From the transition enthalpy it was possible to estimate a, the fraction of liquid crystal contained in the droplets; we found that a decreased with increasing cure temperature, presumably as a result of greater liquid crystal solubility in the epoxy matrix at higher temperatures.     

Thermoplastic polymer‐dispersed liquid crystals prepared from solvent‐induced phase separation with predictions using solubility parameters

The optical effects of liquid crystals can be realized when the mesogens are dispersed in a supporting and stabilizing polymer phase. Thermoplastics were chosen for their structural reversibility and ease of fabrication of polymer‐dispersed liquid crystals (PDLCs) from solution via solvent‐induced phase separation (SIPS). The component match and tuning in PDLCs was achieved in a common solvent through predictions of solubility parameters. The PDLCs were first prepared using SIPS and were then exposed to thermal treatments on a hot stage polarizing microscope or in a differential scanning calorimeter. At elevated temperatures the polymer and mesogen may become miscible, while upon cooling thermally induced phase separation (TIPS) should occur, preferably above the isotropic–nematic transition temperature. The nematic phase existed within disperse phase droplets that were stabilized and supported by the matrix polymer. The temperature range of the nematic phase was extended in the PDLC configuration. The droplet size was important for liquid crystalline optical behaviour. Polymer–mesogen interactions, identified through solubility parameters, were important in ensuring sufficient but not coarse phase separation.     

Propriétés optiques et thermophysiques de composites polyméres-cristaux liquides (PDLC)

Polymer dispersed liquid crystal (PDLC) films can be switched electrically from a light scattering off-state to a highly transparent on-state. Thin films were prepared via a polymerization-induced phase separation process using electron beam radiation. The liquid crystal (LC)/polymer materials were obtained from blends of a eutectic nematic mixture E7 and a polyester acrylate based polymer precursor. The optical and electrooptical properties of the obtained PDLC films strongly depend on the LC concentration. The LC solubility limit in the polymer matrix and the fractional amount of LC contained in the droplets were determined by calorimetric measurements.     

Photopolymerisation kinetics and electro-optical properties in mixtures of dichroic dye-doped nematic liquid crystal and photocurable polymer

This work reports the effect of dye on the photopolymerisation and electro-optical properties of polymer dispersed liquid crystal (PDLC) composite films. Dichroic PDLC (DPDLC) films based on a photocurable polymer and nematic liquid crystal (LC) with an azo dichroic dye were prepared by photopolymerisation-induced phase separation method. Polarising optical microscopy has been used for monitoring the phase separation kinetics and two-phase morphology evolution in the DPDLC system. LC domains with radial structures during initial period of phase separation adopted a resultant morphology of bipolar configuration over the course of polymerisation. The phase separation and morphology of LC domains was found to be dependent on the amount of dye used. Moreover, the addition of small amount of dye reduced the switching voltage, and enhanced the contrast ratio with improved switching time in the PDLC films. It was shown that, under the application of an electric field, the molecular orientation and absorbance of dichroic dye can be controlled in DPDLC to induce non-linearity and colour contrast without the use of polarisers.     

The effect of voltage controlled orientation order of liquid crystals in non-acrylic polymer dispersed liquid crystals films

The nematic liquid crystals (LCs) are randomly dispersed material with random orientation order in polymer dispersed liquid crystal (PDLC) films. The LCs change their orientation from random to vertical as electric field is applied. This transformation of orientation order of nematic liquid crystals in the PDLC films is controlled by many factors operating simultaneously. For instance, some factors like the internal forces of attractions among the neighboring LC molecules, anchoring with polymeric matrix, ITO glass boundaries, and chemical structures of the materials are less studied. The learning of extent of vertical orientation of liquid crystal droplets in an electric field is essential to attain optimum electro optical properties of PDLCs. In this finding, bipolar and radial LCs droplets with random orientation have been observed in non-acrylic polymeric media. It is learned that with small increase of contents of external material, the extent of vertical orientation has been varied intensely. The extent of vertical orientation of LCs molecules increases as the contents of external non-acrylic polymeric material decreased. For this study, the orientations of LCs with respect to material type/contents, external applied force, and restoration of electric filed as hysteresis have been studied in details.     

Transitions of bipolar to radial orientation of liquid crystal droplets in amphiphilic system of PDLC film

The orientation order of nanoscale droplets of thermotropic liquid crystals (LCs) suspended in polymer dispersed liquid crystal (PDLC) solutions prepared with different medias (e.g., polymers, surfactants, nonpolar materials like dyes) respond sensitively and differently via molecular interactions. Such a valuable knowledge provides basis for understanding the properties of PDLC devices. Previously, many studies have explored the droplets size, electro-optical property variations in PDLC films by varying the materials types and its compositions. However, the variations in droplet orientation order with respect to material type and composition provide a new class of study in this particular field. The current study explored the transition in droplet orientation from bipolar to radial on varying the amphiphilic block copolymer concentrations. Further, the variations in surface energies of LCs in different series of block copolymer medias were investigated by contact angle measurements.     

Orientational control of liquid crystal molecules via carbon nanotubes and dichroic dye in polymer dispersed liquid crystal

Polymer dispersed liquid crystals (PDLCs) using nematic liquid crystal and photo-curable polymer (NOA 65) were prepared by polymerisation-induced phase separation technique, in equal ratio (1:1) of polymer and liquid crystal (LC). We demonstrate that doping of small amount (0.125%, wt./wt.) of multiwall carbon nanotubes (CNTs) and orange azo dichroic dye in PDLC generously controlled the molecular orientation, dynamics of LC in droplet and size of droplets. The effects of multiwall CNTs and dye on PDLCs were studied in terms of transition temperature, droplet morphology, transmittance characteristic, contrast ratio and response time. The results exhibited that the values of the threshold electric fields were reduced from 8 V/µm (pure PDLC) to 1.18 and 1.72 V/µm, doped with multiwall CNTs and dye, respectively. The CNTs-doped PDLC shows faster switching response as compared with pure PDLC and dye-doped PDLC. However, dye-doped PDLC shows much higher contrast among all PDLC samples. Further, the results also illustrate that the birefringence value of LC in PDLCs was changed with doping of CNTs and dye.     

Liquid-crystalline epoxies dispersed liquid crystals

Dispersing liquid crystal droplets in a rigid polymer matrix results in an electrically controllable light scattering medium. A polymer with high glass transition temperature phase-separated with a low molecular weight liquid-crystalline material is a good binder for polymer dispersed liquid crystals (PDLC). Main-chain liquid-crystalline epoxies were synthesized for the phase separation with low molecular weight nematic liquid crystals E7 (mixture of 4-alkyl-4′-cyanobiphenyls) and studied for their mesomorphic properties and response to an applied electrical field.     

大分子引发剂分子量对接枝聚合物基体的PDLC电光性能的影响

以可逆加成-断裂链转移(RAFT)、引发转移终止(iniferter)活性自由基聚合相结合的方法,用一步法制备了不同分子量的大分子引发剂RAFT-PS-co-PCMSI(MI),并通过紫外光聚合诱导相分离法制备了以接枝聚合物为基体的聚合物分散液晶(PDLC)膜.研究了不同分子量的MI对PDLC的微观形貌,关闭状态透光率,阈值电压,饱和电压以及记忆效应等方面的影响.研究表明,降低PDLC中MI的分子量,会使得液晶微滴粒径增大,阈值电压(Vth)、饱和电压(Vsat)减小,记忆效应、关闭状态透光率升高.     

Study on the electro-optical properties of polyimide-based polymer-dispersed liquid crystal films

The reflectivity control device, initially developed for attitude control, is utilised to control the solar sail orbit by switching the states between absorption and specular reflection. Actually, the major parts of the device are the polymer-dispersed liquid crystal (PDLC) films. Here, PDLC films based on polyimide (PI) as polymer matrix and a low molecular weight LC can be prepared by the thermally induced phase separation (TIPS) method. The influences of cooling rate and the content of LC on the size and uniformity of LC droplets dispersed in a polymer matrix by a TIPS process were investigated. It was found that a fast cooling rate gave smaller droplet sizes and hence a more uniform distribution as compared to the ones produced under a slow cooling rate. If the LC content was increased, the droplet size would be increased. Furthermore, the effect of LC droplet size on the electro-optical properties of the PI-based PDLC films was discussed, such as transmittance, threshold voltage, driving voltage and contrast ratio (CR).     

The effect of molecular weight of polymer matrix on properties of polymer-dispersed liquid crystals

The electro-optical properties and memory effects are important characters of polymer-dispersed liquid crystal (PDLC) devices. Molecular weight of polymer matrix influences the morphology of liquid crystal droplets in PDLC film and the performance of PDLC devices. In this letter, PDLC films were doped with a small amount of chain transfer agent (CTA), in order to control the molecular weight of polymer matrix. It is observed that the addition of CTA induces a reduction of threshold voltage. In addition, the effect of molecular weight on memory effects of PDLC devices was also discussed. It is found that the entanglement between polymer and liquid crystal molecule increased with the molecular weight, which reduces the memory effect.     

Texture formation under phase ordering and phase separation in polymer-liquid crystal mixtures

Computational modeling of texture formation in coupled phase separation-phase ordering processes in polymer/liquid crystal mixtures is performed using a unified model based on the nematic tensor order parameter and gradient orientation elasticity. The computational methods are able to resolve defect nucleation, defect-defect interactions, and defect-particle interactions, as well as global and local morphological features in the concentration and order parameter spatiotemporal behavior. Biphasic structures corresponding to polymer dispersed liquid crystals (PDLCs), crystalline filled nematic (CFNs), and random filled nematics (RFNs) are captured and analyzed using liquid crystal defect physics and structure factors. Under spinodal decomposition due to concentration fluctuations, the PDLC structure emerges, and the nucleation and repulsive interaction of defects within nematic droplets leads to bipolar nematic droplets. Under spinodal decomposition due to ordering fluctuations, the CFNs structure emerges, and the stable polymer droplet crystal is pinned by a lattice of topological defects. For intermediate cases, where the mixture is unstable to both concentration and nematic order fluctuations, the RFN structure emerges, and polymer droplets and fibrils are pinned by a defect network, whose density increases with the curvature of the polymer-liquid crystal interface. The simulations provide an information of the role of topological defects on phase separation-phase ordering processes in polymer-liquid crystal mixtures.     

Dye-dependent studies on droplet pattern and electro-optic behaviour of polymer dispersed liquid crystal

In order to study the droplet pattern and electro-optic (EO) behaviour of polymer dispersed liquid crystal (PDLC) with the addition of dye, dichroic polymer dispersed liquid crystal (DPDLC) films were prepared using a nematic liquid crystal (NLC), photo-curable polymer (NOA 65) and anthraquinone blue dichroic dye (B2), in equal ratio (1:1) of polymer and liquid crystal (LC) by polymerisation induced phase separation (PIPS) technique. Dichroic dye was taken in different concentration (wt./wt. ratio) as 0.0625%, 0.125%, 0.25%, 0.5% and 1% of the LC mixture in DPDLC films. Initially, in an open circuit when there is no proviso for external electric field (0 V), LC droplets in polymer matrix exhibited bipolar pattern, though on closing the circuit with the increase of electric field pattern of droplets starts changing, LC molecules align along the direction of applied electric field and aligned completely relatively at higher field (30 V), which illustrate vertical radial pattern. Further, results show that the DPDLC film containing 0.0625% dye concentration with consistent average droplet size ~4.30 μm, exhibits the best transmission at lower operating voltage.     

Effect of molecular weight of macro‐iniferter on electro‐optical properties of polymer dispersed liquid crystal films prepared by iniferter polymerization

Polymer dispersed liquid crystal (PDLC) films were prepared by a devised method, in which photo‐polymerization induced phase separation in a mixtures of a macro‐iniferter, methyl acrylater, and liquid crystal. The morphology of the obtained PDLC films was examined on a polarized optical microscopy, and the effect of molecular weight of MIs on the electro‐optical properties was deliberately investigated. Decreasing the molecular weight of MIs in the films led to formation of larger liquid crystal droplets and a lower V_th values. V_sat increased and the memory effect decreased because of the increased interface anchoring strength induced by the higher molecular weight of polymer matrices. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1530–1534, 2009     

A novel polymer dispersed liquid crystal film prepared by reversible addition fragmentation chain transfer polymerization

Polymer as an important component of polymer dispersed liquid crystal (PDLC) has a great influence on electro-optical properties. In this letter, the effect of molecular weight of polymer matrix on the electro-optical properties of PDLC films was investigated with reversible addition fragmentation transfer (RAFT) polymerization. It was found that the saturation voltage and memory effect were apparently influenced by molecular weight of polymer which can be regulated efficiently by irradiation time, while the morphology of liquid crystal droplets kept unaltered. It was estimated that the increase of molecular weight of polymer enhanced entanglement between polymer and liquid crystal, which induced the different surface interaction and electro-optical properties.