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.     

Cyano terminated tolane compounds for polymer dispersed liquid crystal application: relationship between cyano terminated tolane based molecular structures and electro-optical properties

ABSTRACT

The structures of the liquid crystal (LC) molecules have a key role in impacting the electro-optical performance of a polymer dispersed liquid crystal (PDLC) film. In this paper, the relationship between the LC molecular structures and the electro-optical properties of PDLC films is investigated based on an unexplored cyano-terminated tolane compounds (CTTCs) doped E8 LCs/UV polymers system. Due to the high polarity of CTTCs, LCs doped with the cyano-terminated tolane (CTT) molecules exhibit high birefringence and large positive dielectric anisotropy. On the whole, PDLC films doped with the CTT molecules exhibit a lower driving voltage than that doped with the pure E8. More excitingly, PDLC films based on CTT molecules with larger length-to-width ratio and longer conjugated system show higher contrast ratio (CR) and faster response time. Eventually, the mechanism of the effects of CTT-based molecular structures and the relationship between the electro-optical performance of PDLC films and CTT molecules are illustrated. This work paves a new way for optimising the electro-optical properties of PDLC films.     

Effects of the fluorinated liquid crystal molecules on the electro-optical properties of polymer dispersed liquid crystal films

The different fluorinated liquid crystal (LC) molecules doped to E8 were used as LC component to prepare polymer dispersed liquid crystal (PDLC) films. The mass fraction of the LC mixture is fixed 50.0 wt%. Results indicate that doping 8.0 wt% fluorinated LC molecule ME3CP to E8 significantly reduced the driving voltage of the PDLC films, and the driving voltage reduced with the rise of mass fraction of ME3CP. Besides, the terminal flexible chain length of the fluorinated LC molecule influenced the LC mixture properties based on E8, such as the dielectric anisotropy, birefringence and viscosity of the LC mixture, and the morphology and the electro-optical properties of PDLC films were controlled not only by the physical properties of the LC mixture, but also by the terminal flexible chain length of the fluorinated LC molecule .     

固化条件对聚合物分散液晶膜电光性能的影响

选用聚乙二醇二缩水甘油醚(EGDE)/季戊四醇缩水甘油醚(PERTGE)/1,8-二氨基-3,6-二氧杂辛烷(EDBEA)/向列相液晶(SLC1717)复合体系,在不同的固化条件下,通过热聚合诱导相分离方法制备了一系列电光性能不同的聚合物分散液晶(polymer dispersed liquid crystal,简称PDLC)膜.研究了固化温度和固化时间对制备的PDLC膜中聚合物网络的微观形貌和电光性能的影响.结果表明,随着固化温度的升高以及固化时间的缩短,PDLC膜的对比度、驱动电压和开态响应时间逐渐增大,而关态响应时间逐渐减小.在固化温度为363.2 K,固化时间为7 h时,所制备的PDLC膜具有较佳的电光性能.     

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).     

Preparation and electro‐optical properties of polymer dispersed liquid crystal films with relatively low liquid crystal content

In this paper, polymer dispersed liquid crystals (PDLC) films with LC content as low as 40 wt% were prepared, and the electro‐optical properties were carefully investigated. To accomplish this, different (meth)acrylate copolymerizaiton monomers have been used. The electro‐optical properties and morphologies of the PDLC films were strongly influenced by the chemical structure of copolymerization monomers (hydroxypropyl methacrylate (HPMA), glycidyl methacrylate, hydroxypropyl acrylate) and their feed ratio. Lower driven voltage and higher contrast ratio were achieved when the PDLC films showed a morphology with suitably LC domain size. At high HPMA content, a thin polymer film was formed on the surface of PDLC samples, which is beneficial to decrease the total LC content in PDLC devices. Copyright © 2013 John Wiley & Sons, Ltd.     

Studies on electro‐optical properties of polymer matrix/LC/ITO nanoparticles composites

In this paper, polymer‐dispersed liquid crystal (PDLC) films consisting of liquid crystal (LC)/monomers/indium tin oxide (ITO) nanoparticles with good near‐infrared absorption property had been fabricated, and the influence of the ITO nanoparticles modified with 3‐methacryloxypropyltrimethoxysilane (KH570) on the PDLC films was systematically studied. First, different liquid crystal content was studied to obtain PDLC films with good electro‐optical properties. And then, various weight ratio of ITO nanoparticles was added to samples. While the content of ITO nanoparticles was increased, the saturation voltage increased and the CR decreased. Though the electro‐optical properties of PDLC samples reduced with the addition ITO nanoparticles, the near‐infrared absorption property of films was enhanced.     

Comparative studies of polymer‐dispersed liquid crystal films via a thiol‐ene click reaction

In this work, the thiol‐ene click reaction is employed to fabricate polymer‐dispersed liquid crystal (PDLC) films by photoinitiated polymerization. The PDLC films are prepared by systematic variation of key conditions: variety and content of ‐ene monomer, liquid crystal (LC) content, curing time, and curing light intensity. We find that both the morphologies and electro‐optic properties of these films are adjustable. When increasing the length of alkyl main chain of ‐ene monomers, the driving voltages reduce, but in turn, the contrast ratio decreases. Increasing ‐ene monomer content raises the driving voltages as well as the response time, and the increase of LC content lowers the driving voltages but has a negative effect on the contrast ratio. The changes to the curing conditions (both curing time and UV light intensity) can be used to modify the driving voltages, response time, and contrast ratios of PDLC films. These comparative studies will elucidate new insights in commercial applications of intelligent PDLC films.     

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.     

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.     

The physical properties of alkene-terminated liquid crystal molecules/E8 mixture and the electro-optical properties as they doped in polymer-dispersed liquid crystal systems

Effects of the content of fluorinated alkene-terminated liquid crystal (LC) molecules on the physical properties of the fluorinated alkene-terminated LC/E8 mixture were studied. The morphology and electro-optical properties as they doped in polymer-dispersed liquid crystal (PDLC) films were investigated. The detailed discussion of the obtained results is given. As a result, comparing with the physical properties of the series of LC mixtures with the same content of the analogous fully saturated compounds doped with E8, we find that the birefringence is significantly larger for the LC mixture with the alkene-terminated materials. Both fluorinated alkene-terminated LC molecules and the analogous fully saturated compounds doped with E8 reduce the driving voltage of PDLC films. Moreover, PDLC films with the fluorinated alkene-terminated LC molecules possessed higher contrast ratio and faster response time than that of the PDLC films prepared by adding the same mass fraction of the analogous fully saturated compounds. Thus, the ability to manipulate physical properties of LC mixture and electro-optical properties of PDLC films by changing the LC molecular structures may have future relevance for new LC structures design and applications of PDLC films.     

Control of liquid crystal droplet configuration in polymer dispersed liquid crystal with macro-iniferter polystyrene

A polystyrene macro-iniferter was applied to control the alignment of liquid crystal molecules at the droplet wall of polymer dispersed liquid crystal (PDLC) films. The aspects of the alignment were monitored by observing the droplet in the PDLC film. With increasing the macro-iniferter polystyrene in the composition, the configuration of LC droplets changes from bipolar to radial. This is because the high concentration of the macro-iniferter polystyrene results in a small surface interaction between the LC and the polymer matrix, which favours the formation of radial configuration. The radial configuration was stable under our conditions. However, increasing the LC and the initiator concentrations resulted in the change from radial to bipolar.     

Novel techniques of PDLC film preparation furnishing manifold properties in a single device

Three novel techniques of polymer dispersed liquid crystal (PDLC) film preparation have been proposed to obtain/induce systematically varying manifold properties in a single device. These three techniques were used to prepare ‘wedge-shaped’, ‘multi-channelled’ and ‘grating type’ PDLC films. Arrangement and configuration of liquid crystal (LC) microstructures inside these PDLC films, which were conveniently divided into different zones, have been investigated using a polarising optical microscope (POM) and scanning electron microscope (SEM). POM images indicate a predominant bipolar structure in all zones of different types of PDLC films but with varying size and density. Further, the electro-optical (EO) properties of PDLC films for different zones have different morphological characteristics as indicated (observed) in POM and SEM images and were dependent on LC droplet shape, size and distribution. Also different zones show different absorbance/transmittance characteristics in the visible range. Thus, our study proposes a single device with manifold properties. Also, the desired properties can be obtained by selecting the suitable zone from the PDLC composite film.     

An investigation on a novel PDLC film’s fabrication and its electro-optical properties

A polymer dispersed liquid crystal (PDLC) film that has good electro-optical properties is produced by the method of polymerized-induced phase separation. Based on the application foreground, its capability parameters, such as contrast ratio, work voltage, and visual angle, are characterized for the first time by a white light but not a fixed wavelength light. The results show the PDLC film has a low work-voltage of 20 V, more than 150° visual angle, high stability, and long lifetime. The differences between plastic and glass ITO-coated substrates of PDLC films are also studied in this paper. The plastic substrate has better property and will have a wider perspective especially in the portable, tender and folded display devices. Due to adjustable properties of film by electric field, PDLC has the potential application for display device, sensor, switch, grating, and new generation analytical apparatus.     

Morphology of epoxy/acrylic polymer‐dispersed liquid‐crystal film in DICY thermal cure

A polymer‐dispersed liquid‐crystal (PDLC) film was prepared from UV‐curable acrylic, thermally curable epoxy, and a liquid‐crystal (LC) mixture with a fixed LC content of 40 wt %. The UV irradiation and heat treatments were in sequential steps. At first, a phase diagram of a binary mixture of LC (E63) and epoxy [diglycidyl ether of polypropylene glycol (DER736)] was established to understand their miscibility. Then, the phase‐separation temperatures and morphologies of pre‐UV‐cured films with different equivalent DER736/dicyandiamide (DICY) molar ratios were observed. Finally, the polymerization‐induced phase‐separation behavior and morphology of the PDLC film were studied by real‐time observation while the film was maintained at 130 °C under the microscope. The results showed that the acrylic network would not affect the phase‐separation behavior of the E63/DER736 mixture. In both thermally induced and polymerization‐induced phase separations, the undissolved DICY particles acted as nucleation agents and were capable of inducing E63 to separate out early. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2033–2042, 2000     

Studies on the electro-optical and the light-scattering properties of PDLC films with the size gradient of the LC droplets

Polymer dispersed liquid crystal (PDLC) films with the size gradient of the LC droplets were prepared based on the epoxy/acrylate hybrid polymer matrix. The ultraviolet (UV) intensity gradient was induced by the UV-absorbing dye over the thickness of the samples. Taking advantage of the difference between the epoxy monomers and acrylate monomers in polymerisation rates and the UV intensity gradient, the gradient distribution of the LC droplet size was formed in PDLC films. The effect of the size gradient of the LC droplets on the electro-optical and the light-scattering properties of PDLC films was investigated. The results showed that due to the size gradient distribution of the LC droplets, PDLC films could exhibit the strong light scattering in the UV-visible-near infrared (VIS-NIR) region. Consequently, it provides a potential approach for modulating NIR light transmittance.     

TSC study and electro‐optical properties of epoxy/acrylic polymer‐dispersed liquid‐crystal film in DICY thermal cure

We report on the structures and electro‐optical properties of epoxy/acrylic polymer‐dispersed liquid‐crystal (PDLC) films. A thermal stimulated current (TSC) analysis was used to investigate the physical structures of PDLC. In the TSC spectrum of PDLC, three relaxation peaks were observed: the glass transition of the liquid crystal, the glass transition of the polymer matrix, and the ρ transition. The ρ transition represents the discharge behavior of space charges, and its intensity increased as the curing time and content of the curing agent dicyandiamide (DICY) increased. The pre‐UV‐cured films with different DICY contents were thermally cured at 130 °C for various periods. The electro‐optical properties of PDLC, such as the contrast ratio and switching voltage, increased as the curing time of DICY, the content of DICY, or both increased. As the ambient temperature increased from 10 to 40 °C, the contrast ratio and switching voltage of PDLC gradually decreased. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 507–514, 2001     

The effect of mono-sized liquid crystal domains on electro-optical properties in a polymer dispersed liquid crystal prepared by using monodisperse poly(methylmethacrylate)/liquid crystal microcapsules

Highly mono-sized poly(methyl methacrylate) (PMMA)/liquid crystal (LC) microcapsules having a mono-sized single LC domain were prepared by the solute codiffusion method and solvent evaporation. The size of the LC domain in the microcapsules could be controlled by the amount of LC introduced during the swelling stage. The electro-optical properties of the polymer dispersed liquid crystal (PDLC) prepared by using the microcapsules was highly improved. In particular, the threshold voltage was lowered and the switching behaviour with an applied electric field was sharpened drastically compared with PDLC prepared simply by solvent evaporation-induced phase separation.     

The fabrication of novel optical diffusers based on UV-cured polymer dispersed liquid crystals

Polymer dispersed liquid crystals (PDLCs) with different sizes of the LC droplets are prepared based on the ultraviolet (UV) light curable acrylate monomers/LCs composites to fabricate the optical diffuser films. To acquire light diffusers with high optical performance, the effects of the monomer structure and the UV light intensity on the micro-structure of the PDLC films are studied. Results show that the PDLC films could exhibit a strong light scattering at the premise of maintaining high transmittance in the visible region. As the LC droplets are spherically dispersed in the polymer networks, when the size of LC droplets is about 3.0 μm, the haze can reach 88.5% and the transmittance is nearly 90.0%, which can be used as a bottom diffuser film. While when the size of LC droplets is about 10.0 μm, the haze and transmittance are 39.2% and 90.2%, respectively; hence, it can be a good choice for a top diffuser film. With the advantages of simple preparation, roll-to-roll industrial production and tunable optical properties, it is supported that the films based on UV-cured PDLC films can be applied as outstanding optical diffuser films in the liquid crystal display industry.     

Control of the microstructure of polymer network and effects of the microstructures on light scattering properties of UV‐cured polymer‐dispersed liquid crystal films

Polymer‐dispersed liquid crystals (PDLC) films were prepared from ultraviolet (UV) irradiation‐induced polymerization of the photopolymerizable monomers in photopolymerizable monomers/nematic liquid crystal (LC) mixtures. The effects of the composition of the mixtures, the curing temperature, and the UV light intensity on the microstructure of the polymer network in the PDLC films were investigated. Furthermore, the effects of the microstructures on the light scattering properties of the PDLC films in the wavelength region of 300–2500 nm were studied experimentally and theoretically based on the combination of three kinds of classical light scattering theories: the Rayleigh‐Gans (RG) approach, the anomalous diffraction (AD) approach, and the geometrical optics (GO) approach. It was found that the sizes of LC domain in PDLC films increased with the increase of the LC content as well as the decrease of the UV curing intensity, while increased at first and then decreased with the increase of the curing temperature. Moreover, smaller LC domain sizes could exhibit strong scattering properties in a smaller VIS wavelength region and the transmittance in NIR region (especially in the wavelength range of 1300–2500 nm) obviously decreased with the increasing sizes of LC domain. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2090–2099, 2008