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.     

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.     

Modification of electro-optical properties of polymer dispersed liquid crystal films by iniferter polymerization

In this letter, iniferter polymerization was employed to prepare polymer dispersed liquid crystal (PDLC) films. Polystyrene (PS) was prepared as a macro-iniferter (MI). With the addition of MI in PDLC films, poly(methyl acrylate)-b-polystyrene was prepared in situ and used as polymer matrix in photopolymerization induced phase separation (PIPS). A reduction in driving voltages and an improvement in the ON state transmittance were observed for the sample prepared with a small amount of MI; while a poor electro-optical performance was obtained for that without any MI. Moreover, molecular weight and refractive index of the polymer matrix could be easily adjusted by the concentration of MI, and the matrix seems to be a prospective material for the PDLC devices.     

多官能Iniferter制备聚合物分散液晶膜及其含量对电光性能的影响

采用可逆加成-断裂链转移(RAFT)、引发转移终止(Iniferter)活性自由基聚合法分步骤制备多官能Iniferter的大分子(RAFT-MI),并通过紫外光聚合诱导相分离法制备接枝共聚物为基体的聚合物分散液晶(PDLC)膜,研究了不同含量的RAFT-MI对PDLC膜的微观形貌、开态透光率、阈值电压(Vth)、饱和电压(Vsat)、对比度和记忆效应的影响.结果表明,当PDLC中的RAFT-MI含量从10%增加到30%时,开态透光率先增加,随后又逐渐降低,而Vth、Vsat逐渐降低,对比度先增加,然后又降低,记忆效应减弱.     

聚合物分散液晶膜

聚合物分散液晶膜是将液晶和聚合物结合,得到的一种综合性能优异的膜材料,液晶分子赋予了聚合物分散液晶膜显著的电光特性,使其受到了广泛的研究,并有着广阔的应用前景。而聚合物作为成膜材料,起着辅助但是重要的作用,其结构和固化过程是影响聚合物分散液晶膜电光特性的重要因素。本文简要综述了聚合物分散液晶膜的制备方法、电光特性的影响因素及研究手段。     

<Superscript>2</Superscript>H-NMR investigation after a polymerisation-induced phase separation process*

Polymer-dispersed liquid crystals (PDLC) are composite materials consisting of micron-sized droplets of liquid crystal dispersed in a polymer matrix. The easiest method to obtain a PDLC film is the polymerisation-induced phase separation process (PIPS). The liquid crystal is mixed with a monomer of low molecular weight and polymerisation is induced by heat or UV light. The increasing molecular weight of the polymer causes the phase separation of liquid crystal from the polymer matrix as micron-sized droplets. In this work, we have studied the structural changes induced in the polymer matrix of a PDLC after the PIPS process by deuterium nuclear magnetic resonance. Two different selectively deuterated monomers have been synthesized and investigated: isobutyl methacrylate (IBMA-d₂) and methyl methacrylate (MMA-d₃). The main results were the disappearance of the characteristic two-site hop in poly-IBMA, due to liquid crystal molecules, and the lack of unreacted MMA molecules in the liquid crystal droplets. In this last case, we found that it is possible to confine temporarily the unreacted MMA molecules within liquid crystal droplets.Abbreviations MMA Methyl methacrylate - IBMA Isobutyl methacrylate - PDLC Polymer-dispersed liquid crystal - PIPS Polymerisation-induced phase separation - ²H-NMR Deuterium nuclear magnetic resonance*Dedicated to Professor V. Bertini for his 70^th birthday     

Influence of chain length of prepolymers in permanent memory effect of PDLC assessed by solid-state NMR

ABSTRACT

The relationship between linear chain (ethylene oxide units) length of polymerisable monomers with morphology, electro-optical properties and ¹³C nuclear magnetic resonance (NMR) spectroscopy of the corresponding polymer-dispersed liquid crystal (PDLC) films was investigated. The preferred liquid crystal molecule alignment and permanent memory effect of PDLC were greatly influenced by the length of the molecular chain of prepolymers to be incorporated as a polymer matrix. By increasing the number of ethylene oxide in prepolymer chain and maintaining the number of functionalities (polymerisable groups in each monomer molecule), the permanent memory effect of PDLC increased, as proved by solid-state ¹³C NMR spectroscopy.     

Improvement of permanent memory effect in PDLC films using TX-100 as an additive

A number of polymer dispersed liquid crystal (PDLC) films based on dimethacrylate monomers were synthesised by polymer-induced phase separation (PIPS) using polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether (TX-100) as an additive up to total solution weight of 10% aiming to modify the initial anchorage force of the liquid crystal (LC) molecules to the polymeric matrix. The effects of the addition of this additive to the PDLC films were studied resorting to electro-optical studies. Using a fitting model, several parameters were correlated such as the permanent memory effect (PME), the voltage required to achieve 90% of maximum transmittance (E90), the average elastic constant (K) and the rotational viscosity of the director (γ). The use of TX-100 results on an increase on the PME and γ, and decrease on the E90 and K.     

Thermotropic and optical behaviour of new PDLC systems based on a polysulfone matrix and a cyanoazomethine liquid crystal

The thermotropic and optical characterisations of a novel polymer dispersed liquid crystal (PDLC) system based on polysulfone UDEL P-1700 as polymer matrix and a low molecular weight liquid crystal compound containing a mesogenic azomethine core and a cyano-substituent were investigated. The PDLC samples were prepared by solvent-induced phase separation (SIPS) and thermally induced phase separation (TIPS) methods using various compositions in the two components. Information on the morphology and phase structure was obtained by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. PDLC systems with well-defined droplets were obtained for the composite with medium content of liquid crystal compound. The optical characterisation of these materials was performed by analysing their UV–visible absorption and photoluminescence emission as a function of the liquid crystal aggregation degree.     

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     

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.     

The investigation of molecular affinity involved in poly(ethylene glycol)-based polymer-dispersed liquid crystal display

Acrylic polyethylene glycol(PEG)-based polymer-dispersed liquid crystal (PDLC) films have been fabricated to investigate the effect of intermolecular interactions on PDLC performance. For this purpose, the amphiphilic liquid crystal and polymers are selected as PDLC composite materials. The acrylic PEG contents are varied from 0 to 66.66 mol wt.% in order to understand the effects of different levels of additions on the microstructure and electro-optical properties of the PDLC films. For this intention, polarized optical microscopy and UV–vis spectroscopy are used. The extent of phase separation and anchoring energy are also examined using Fourier transform infrared (FTIR) spectroscopy and contact angle measurements in consequence of acrylic PEG addition. The contrast ratio, threshold voltage, as well as saturation voltage, tended to increase with the addition of acrylic PEG. The molecular affinity involved in the polymer matrix and LC molecules affected the phase separation which is responsible for the formation of domain size; this accordingly changed the electro-optical properties of PDLC film.     

A study on the polymer structures and electro-optical properties of epoxy-mercaptan-based polymer dispersed liquid crystal films

ABSTRACT

In this paper, polymer dispersed liquid crystal (PDLC) films based on epoxy-mercaptan system were prepared by thermal-initiated polymerization. The effects of the liquid crystal (LC) content, the proportion and the functionality of epoxy monomers on the polymer structures and electro-optical properties of the as-made PDLC films were investigated systematically. It was found that the morphologies of the polymer matrix can be altered from polymer meshes to polymer balls by increasing the LC content as well as the functionality of epoxy monomers. Accordingly, the electro-optical properties could be regulated by the morphologies of polymer networks. Especially, the as-made PDLC films with homogeneous porous structures exhibited the optimal electro-optical properties. Consequently, this work offers a meaningful approach to control the microstructures and optimize the electro-optical properties of PDLC films, which indeed can form a wonderful footstone for the wide application of PDLC.     

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).     

Digital optical memory devices based on polymer-dispersed liquid crystals films: appropriate polymer matrix morphology

ABSTRACT

Permanent memory effect (PME) in polymer dispersed liquid crystal (PDLC) allows a greater applicability range than traditional PDLCs. One of the most interesting application could be the possible storing of optical information, the so-called Digital Optical Memory (DOM) devices. To test this application it would be required a display structure having an array of pixels addresses. Each pixel was filled with PDLC film with PME and electric field can be independently applied to different PDLC elements to define on/off pixel states (transparent or scattering states).PDLC films were obtained from a mixture of E7 nematic liquid crystal and poly(ethylene glycol) dimethacrylate with 875 g mol^-1oligomer as precursor of the polymeric matrix. The effect of the curing temperature and the UV light intensity as well time exposure during the polymerisations on the electro-optical performance of PDLC films were investigated. In this way, a high transparency state (T_OFF=55%) for a long period of time at room temperature even after the applied voltage has been switched off were obtained, started from an opaque state (T₀=0%) and after reaching a transparent state (T_MAX=75%), which causes 73% PME. The application to an 8x8 passive matrix using PDLC with PME is also demonstrated as proof-of-principle.     

Temperature dependence of electro-optical characteristics of polymer dispersed liquid crystal films

Polymer dispersed liquid crystal (PDLC) films consist of microdroplets of a liquid crystal dispersed in a polymer matrix. Their applications are based on the electrically controllable light scattering properties of the liquid crystal droplets. The effects of temperature on the electro-optical properties of PDLC films have been rarely investigated. In this work, we studied the light transmission on varying the temperature and frequency. It was observed that the transmission at a fixed voltage decreased with increasing temperature above 43°C, independent of frequency. We examined possible origins of this unusual dependence of the transmission on the temperature. It was concluded that conductivity effects due to free ions newly created at high temperatures could be responsible for the unusual behaviour observed.     

Temperature dependence of electro-optical characteristics of polymer dispersed liquid crystal films

Polymer dispersed liquid crystal (PDLC) films consist of microdroplets of a liquid crystal dispersed in a polymer matrix. Their applications are based on the electrically controllable light scattering properties of the liquid crystal droplets. The effects of temperature on the electro-optical properties of PDLC films have been rarely investigated. In this work, we studied the light transmission on varying the temperature and frequency. It was observed that the transmission at a fixed voltage decreased with increasing temperature above 43°C, independent of frequency. We examined possible origins of this unusual dependence of the transmission on the temperature. It was concluded that conductivity effects due to free ions newly created at high temperatures could be responsible for the unusual behaviour observed.     

The fabrication of polymer dispersed liquid crystal based on SiO2 photonic crystal template

The conductance of polymer matrix is an important factor for the property of the polymer dispersed liquid crystal (PDLC). The nanographites are dispersed into the polymer matrix for optimising the dielectric conductive property. The synthesised nanoparticles SiO₂ was used as photonic crystal (PC) to work as a template for fabricating PDLC films. A mixture of pre-polymer and liquid crystals (LCs) was infiltrated into the void of the PC and polymerised under ultraviolet light. The void of the PC made uniform the dispersion of the liquid crystals in the films. The optical property of the PDLC films was optimised by doped nanographites and negative charge SiO₂ template. The effect of negative charge SiO₂ and nanographites on the threshold voltage and driving voltage was researched. The morphology of the PDLC films was studied by the FTIR image. The dispersed LCs droplets were uniformly affected by the addition of the nanographites. The LCs droplets dispersed in the polymer were located in the void of the SiO₂ photonic crystal.     

UV tuning of the electro-optical and morphology properties in polymer-dispersed liquid crystals

Polymer-dispersed liquid crystal (PDLC) films operating in reverse mode are transparent electro-optical devices, which can be turned into an opaque state by application of a suitable electric field. The effect was investigated of different UV powers, used during the polymerization process, on the electro-optical and morphology properties of PDLCs, working in reverse mode operation. Films were obtained by UV polymerization of mixtures of a low molecular weight nematic liquid crystal and a photopolymerizable liquid crystal monomer, homeotropically aligned by rough conductive surfaces. The electro-optical and morphology properties of samples were related to the polymerization conditions. Samples polymerized by lower UV powers exhibited “polymer ball” morphology and an electro-optical response due to the liquid crystal director reorientation, whereas samples obtained at higher UV powers showed a “Swiss cheese” morphology and an electro-optical response due to dynamic scattering. In addition, we observed by conductivity and IR measurements that UV exposure induces a degradation of the nematic liquid crystal.     

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.