Impact of co-doping concentration in copolymer network liquid crystals

ABSTRACT

The impact of varying the co-doping concentration of a mesogenic and a non-mesogenic monomer in the reactive mixtures used to create a copolymer network LCs was investigated. Use of copolymer has been found to improve the response properties in the obtained liquid crystal composites. The polymer network in the studied copolymer network LCs was examined by scanning electron microscopy and the response times in various samples were investigated. Samples were prepared with various reactive mixtures, each of which had a constant concentration of mesogenic monomer, various concentrations of non-mesogenic monomer, and the same amount of photoinitiator. These reactive mixtures were filled in home assembled test cells with planar alignment and then exposed to UV light. With increasing concentration of the non-mesogenic monomer, the response properties of the resulting copolymer network LC were improved. Usually, if the overall polymer content in a polymer network LC is increased, the threshold voltage is also increased. However, both threshold voltages and response times were lowered and the response properties were thus improved in the studied copolymer network LCs. This unexpected behavior could be traced back to inducing a grainy polymer morphology of the copolymer network by using a non-mesogenic monomer.     

Dynamic ordering transitions of liquid crystals driven by interfacial complexes formed between polyanions and amphiphilic polyamines

We report the design of an amphiphilic polyamine (polymer 1) based on poly(2-alkenyl azlactone) that strongly couples the formation of polyelectrolyte complexes at aqueous/liquid crystal (LC) interfaces to ordering transitions in the LC. We demonstrate that the addition of a strong anionic polyelectrolyte to aqueous solutions in contact with polymer 1-laden LC interfaces (prepared by Langmuir-Schaefer transfer of monolayers of polymer 1 onto micrometer-thick films of nematic LC) triggers ordering transitions in the LCs. We further demonstrate that changes in the ordering of the LCs (i) are driven by electrostatic interactions between the polyelectrolytes, (ii) involve multivalent interactions between the polyelectrolytes, and (iii) are triggered by reorganization of the hydrophobic side chains of amphiphilic polymer 1 upon formation of the interfacial complexes. The results presented in this paper lead us to conclude that ordering transitions in LCs can be used to provide insights into the structure and dynamics of interfacial complexes formed between polyelectrolytes.     

An electrically controlled light-scattering device based on liquid crystal/polymer microsphere composites

ABSTRACT

There is a widely applied prospect of electrical controlled liquid crystal (LC) light-scattering device. Numerous electrical controlled LC light-scattering technologies have been studied, but each technology has its own shortcomings, such as high driving voltage, high hysteresis, complex electrode structure, and serious heating. In this work, the composite of LC and polymer microspheres are used to fabricate light-scattering devices. This device is operated by the vertical electric field and does not require complex preparation process. LC/polymer microsphere composite has the advantages of low driving voltage and zero hysteresis. The role of microspheres in the composites is to change the size and density of a refractive-index-mismatched micro-domain. The effects of the ratio, particle size, and refractive index of microspheres on the optical characteristics of a composite are studied. The normal directional light transmittance at the transparent state and light-scattering state decreases with an increasing weight ratio of microspheres. The particle size of microspheres has negligible influence on the electro-optical properties of composites when the weight ratio of microspheres is small. The LCs doped with Polymethylsilsesquioxane (PMSQ) microspheres or polymethyl methacrylate (PMMA) microspheres are compared, and the mismatched refractive index and density of micro-domain show the influence on the electro-optical properties of the composites.     

Biphenyl-based liquid crystals for elevated temperature processing with polymers

Due to the limited thermal stability of current commercially available liquid crystals (LCs), the incorporation into polymer composites through standard processing techniques, such as melt coextrusion, has been hindered. Motivated by this dilemma, a series of smectic B liquid crystalline structures based on the 4,4?-alkyl substituted biphenyl moiety were synthesised through conventional methodologies and probed for their thermal stability and LC properties. Degradation temperatures were found to increase with increasing aliphatic chain length – up to 295 °C for C16 substituted structures, which is well above the processing temperatures of commercial polymers. Additionally, all compounds were found to be liquid crystalline in nature with crystal-to-smectic B transition temperatures ranging from 49.8 °C to 91.4 °C. Thermal stability, phase separation, and compatibility of LC/polystyrene composites were also examined. Less than 10% of 15A15 LC by weight in polystyrene exhibited good polymer miscibility, while phase separation occurred at loads higher than 15% by weight. We foresee the use of these LCs in applications that require elevated processing conditions to produce materials with enhanced mechanical or gas barrier properties.     

Achieving a robust homogenously aligned liquid crystal layer with reactive mesogen for in-plane switching liquid crystal displays

Uniformly aligned liquid crystals (LCs) are of crucial importance in a practical application, such as displays, phase modulators and virtual reality devices. Although an alignment layer using polyimide-type polymers can almost perfectly align the LCs, polymer-stabilisation at the surface using pre-mixed monomers has been attempted to reduce the fabrication process, i.e. eliminating the alignment layer, thereby reducing the fabrication cost. Here, we propose an approach to achieve a homogeneous alignment of LCs by controlling the molecular structure of reactive monomers mixed in LCs without using conventional polyimide alignment layer. The result shows an excellent initial dark state and acceptable electro-optic performance which implies that the polymer stabilisation at the surface successfully anchors the homogenous orientation of LCs. We believe that the proposed fabrication method can contribute to cost-effective fabrication process by eliminating an alignment layer with no fabrication step of a surface treatment.     

全息聚合物分散液晶的结构调控与性能

全息聚合物分散液晶(HPDLCs)是由富聚合物相与富液晶相周期性排列而成的结构有序高分子复合材料.HPDLCs通过单体/液晶复合体系的光聚合诱导相分离而形成,如何调控并定量化描述复合体系的光聚合反应动力学、凝胶化行为和相分离程度,进而获得结构规整、电光性能优异的HPDLCs是关键难题.专论概述了光引发体系、单体结构、纳米无机材料掺杂对HPDLCs结构及性能的影响.光引发阻聚剂通过引发和阻聚的竞争与协同,降低了光聚合反应速率、延迟了凝胶时间,促进形成衍射效率达90%的HPDLCs.超支化单体降低了复合体系黏度和光聚合反应速率,延迟了凝胶时间,促使形成衍射效率达94%、具有一维光子晶体结构的HPDLCs.丙烯酰胺单体优化了相分离结构,将HPDLCs的衍射效率提升至98%.纳米硫化锌掺杂在保持规整结构和高衍射效率的同时,大幅降低了HPDLCs的驱动电压.研究还确定了HPDLCs的相分离程度与凝胶时间的函数关系.构建兼具高衍射效率与低驱动电压的HPDLCs,推进其在彩色3D图像存储等领域的应用仍是重要课题.     

UV-driven switching of chain orientation and liquid crystal alignment in nanoscale thin films of a novel polyimide bearing stilbene moieties in the backbone

A novel photosensitive polyimide, poly(4,4'-stilbenylene 4,4'-oxidiphthalimide) (ODPA-Stilbene PSPI) was newly synthesized. The most surprising feature of this PSPI is that the PSPI films irradiated with linear polarized ultraviolet light (LPUVL) can favorably induce a unidirectional alignment of liquid crystals (LCs) in contact with the film surface and further switch the director of the unidirectionally aligned LCs from a perpendicular direction to a parallel direction with respect to the polarization direction of LPUVL by simply controlling the exposure dose in the irradiation process. These LPUVL-irradiated films were found to provide high anchoring energy to LCs, always giving very stable, homogeneous cells with unidirectionally aligned LCs regardless of the LC alignment directions. In the films, the PSPI polymer chains were found to undergo favorably unidirectional orientation via a specific orientation sequence of the polymer chain segments led by the directionally selective trans-cis photoisomerization of the stilbene chromophore units in the backbone induced by LPUVL exposure. Such unidirectionally oriented polymer chains of the films induce alignment of the LCs along the orientation direction of the polymer chains via favorable anisotropic molecular interactions between the oriented polymer chain segments and the LC molecules. In addition, the PSPI has an excellent film formation processibility; good quality PSPI thin films with a smooth surface are easily produced by simple spin-coating of the soluble poly(amic acid) precursor and subsequent thermal imidization process. In summary, this new PSPI is the promising LC alignment layer candidate with rubbing-free processing for the production of advanced LC display devices, including LC display televisions with large display areas.     

高分子导热复合材料结构设计及性能研究进展

近年来,电子设备的需求逐渐向集成化、微型化发展,随之带来了愈发严重的发热问题已经成为了阻碍电子设备发展的重要因素之一。作为电子设备重要组成材料之一的高分子材料对优良导热性能的要求也越来越高,导热高分子复合材料的研究已经成为当前功能复合材料的重要发展方向。本文综述了高分子导热复合材料的发展趋势,介绍了当前选用填料法来制备单一填料、混杂填料高分子导热复合材料以及双逾渗结构、隔离结构等复杂多相结构的高分子导热复合材料的研究进展。重点介绍了通过多种导热填料的组合利用来制备高性能导热高分子复合材料。最后,对填料法高导热高分子复合材料的发展方向做出了简要展望。     

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.     

Structural design and impact resistance of three-dimensional structure-reinforced flexible polymer composites

Three-dimensional (3D) structure-reinforced flexible polymer composites have great potential as personal protective materials. These composites exhibit excellent mechanical properties and failure mechanisms than typical rigid composites because of the complex dynamic reaction processes caused by the 3D structure in response to impact. This paper comprehensively reviews the impact resistance mechanism of 3D structure-reinforced flexible polymer composites by combining current results with relevant investigations. 3D woven fabric reinforcements and flexible matrix materials of flexible polymer composites systems are presented in this paper. The classification for 3D woven fabric reinforcements is reviewed, as well as the effect of reinforcement structures on the impact resistance of the flexible composites. Furthermore, several flexible matrix are introduced. Several external factors affecting the impact resistance of composites are then discussed. Finally, the impact damage mechanism of 3D structure-reinforced flexible polymer composites is summarized and analyzed.     

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.     

A novel method for encapsulation of a liquid crystal in monodisperse micron-sized polymer particles

Liquid crystals (LCs) encapsulated in monodisperse micron-sized polymer particles were prepared to control the size and size distribution of LC droplets in polymer-dispersed LCs. The poly(methyl methacrylate) (PMMA) seed particles were swollen with the mixture of liquid crystal, monomers (methyl methacrylate and styrene) and initiator by using a diffusion-controlled swelling method. A single LC domain was produced by the phase separation between PMMA and LC through polymerization. The optical microscopy and scanning electron microscopy showed that the particles are highly monodisperse with core–shell structure. Moreover, monodisperse LC core domains were confirmed from polarized optical microscope observations. The final particle morphology was influenced by the cross-linking of the seed particle. When linear PMMA particles, which are not cross-linked, were used as a seed, the microcapsules were distorted after annealing for a few days; however, in the case of cross-linked PMMA particles, the core–shell structure was sustained stably after annealing. Received: 22 November 2000 Accepted: 12 March 2001     

Detection of mRNA from Escherichia coli in drinking water on nanostructured polymeric surfaces using liquid crystals

In this study, we demonstrate the detection of mRNA from Escherichia coli in drinking water using thermotropic liquid crystals (LCs). After hybridization of complementary mRNA with the single-stranded DNA immobilized on a polymer substrate containing periodic sinusoidal wave patterns, the orientation of LCs transits from a uniform to a non-uniform state, thereby inducing a change in the optical response of LCs. The periodic sinusoidal features of the polymer substrate are obtained through buckling the poly-(dimethylsiloxane) slide on a cylindrical surface, followed by replicating the associated relief structures on a poly-(urethaneacrylate) surface, where a film of gold was deposited. Then, thiol-modified single-stranded DNA was functionalized on the gold film as an mRNA receptor. The formation of mRNA–single-stranded DNA complex, which covers the sinusoidal nanostructures on the surface, induces the orientational transition of LCs. This result indicates that LCs can be used to report the specific hybridization of mRNA with single-stranded DNA, which holds promise for the sensitive and label-free detection of viable bacterial pathogens in drinking water.

LDPE／CPE／炭黑三相复合导电体系的亚微形态和导电性能

对ＬＤＰＥ／ＣＰＥ／炭黑三相复合导电体系的亚微形态和导电性能进行了研究。实验发现,该体系的亚微形态在共混比ＬＤＰＥ／ＣＰＥ大于和小于５０／５０时为典型的“海－岛”结构,在５０／５０时,为两相连续交错“互锁”结构;在共混比大于５０／５０时,ＬＤＰＥ／ＣＰＥ炭黑复合体系的导电性能较单一的ＬＰＤＰＥ树脂与炭黑复合体系的高２－５个数量级。     

Threading Chalcogenide Layers with Polymer Chains

Inserting polymers into a crystalline inorganic matrix to understand the structure, position, and the structure–property relationships of the resulting composites is important for designing new inorganic‐organic materials and tuning their properties. Single crystals of polymer‐chalcogenide composites were successfully prepared by trapping polyethyleneglycol within a selenidostannate matrix under surfactant‐thermal conditions. This work might provide a new strategy for preparing novel crystalline polymer‐inorganic composites through encapsulating polymer chains within inorganic matrices.     

EFFECT OF T-ZnOw DIMENSION ON PROPERTIES OF T-ZnOw/PA6 COMPOSITES

As a part of serial work about the application of a tetra-needle-shaped whisker(T-ZnOw) with a spatial structure in polymer composites,this work is focused on the effect of T-ZnOw dimension on the properties of polymer composites. Two kinds of T-ZnOw whiskers with different dimensions(big and small one) are introduced into PA6 composites.Our results show that for the big whisker and the small whisker both,the addition of T-ZnOw induces the mechanical property improvement of T-ZnOw/PA6 composites.Especial...     

Chemical and structural modification of polymers by matrix polymerization

The condensation polymerization of urea and formaldehyde in water in the presence of a macromolecular matrix, polyacrylic acid, as well as properties of composites obtained by the matrix polymerization, have been studied. The chemical structure of the urea-formaldehyde polymer was changed by the presence of the matrix. The products of matrix polymerization are composites consisting of a stoichiometric polycomplex of polyacrylic acid with the urea-formaldehyde polymer and an excess of one of the components, depending on the initial composition of the system. Introduction of matrix macromolecules into the reacting system leads to a fibrillized structure of the urea-formaldehyde polymer. The polycomplex, as well as composites with high content of polyacrylic acid, are glasses characterized by high compressive strength and ability to forced elastic deformation. They swell in water. The highly cooperative character of potentiometric titration curves for swollen gels and the quantitative yield in intermolecular amidation indicate an ideal structure of the polycomplex stabilized by hydrogen and ionic-type bonds.     

聚吡咯/聚合物固体电解质双层复合膜研究

在聚合物固体电解质（聚乙二醇不饱和聚酯网络－LiClO4)中进行吡咯聚合原位制得了聚吡咯／聚合物固体电解质双层复合膜。用扫描电镜观察复合膜的界面结构,用循环伏安和交流阻抗法研究了复合膜的电化学杂脱掺杂性能。结果表明,聚吡咯／聚合物固体电解质双层复合膜具有相互穿插渗透的固／固密接界面结构,这种界面结构改善了聚吡咯和聚俣物固体电解质间的界面接触,提高了聚吡咯在聚俣物固体电解质中的电化学掺杂脱掺杂性能。     

高分子基导电复合材料气敏响应机理研究

高分子基气敏导电材料是近年来发展起来的一种新型功能高分子复合材料.本文介绍了以炭黑(CB)为导电填充剂的复合传感材料的气敏响应机理的体积膨胀模型、结晶模型和氢键模型,并讨论了逾渗阀值、CB及聚合物微观结构与性能、以及CB与聚合物和溶剂三者之间相互作用等因素对该类材料气敏响应性的影响.     

INVESTIGATION OF STRUCTURE AND PROPERTIES FOR POLYMER SYSTEMS BASED ON DYNAMIC RHEOLOGICAL APPROACHES

The dynamic theological measurements have been a preferred approach to the characterization of the structure and properties for multi-component or multi-phase polymer systems, due to its sensitive response to changes of structure for these heterogeneous polymers. In the present article, recent progresses in the studies on dynamic theology for heterogeneous polymer systems including polymeric composites filled with inorganic particles, thermo-oxidized polyolefins, phaseseparated polymeric blends and functional polymers with the scaling and percolation behavior are reviewed, mainly depending on the results by the authors‘ group. By means of theological measurements, not only some new fingerprints responsible for the evolution of morphology and structure concerning these polymer systems are obtained, the corresponding results are also significant for the design and preparation of novel polymer-based composites and functional materials.