丙烯酸酯/液晶体系的光聚合反应动力学对PDLC电光性质的影响

采用光-示差扫描量热法(P-DSC)和光-流变学(P-Rheology)技术,测定了丙烯酸酯/液晶体系的光聚合反应动力学和凝胶化时间.基于自催化模型和凝胶时间-温度关系,计算了体系的光聚合反应速率常数和活化能,探讨了单体结构与组成、反应温度对体系光聚合动力学的影响,并研究了聚合物分散液晶(PDLC)的电光响应行为与相分离结构对光聚合动力学的依赖性.结果表明,升高反应温度、增加体系的单体反应活性和平均官能度,均提高了体系的光聚合速率常数,缩短了光聚合凝胶时间.随着单体反应活性和平均官能度的提高,体系的光聚合反应活化能明显降低,且凝胶化前的光聚合反应活化能低于光聚合全过程的平均反应活化能.当液晶含量为50%时,形成的PDLC呈亚微米尺度的双连续相结构.随着光聚合反应温度的升高,光聚合速率加快,导致凝胶时间缩短、相分离程度降低,使PDLC中液晶相尺寸变小、聚合物网络致密化,PDLC的弛豫时间延长、饱和电压降低,而开启时间和阈值电压变化不大.     

基于偶氮液晶的PDLC膜光调制研究

采用聚苯乙烯和光敏混合向列液晶(5CB＋BMAB), 通过溶剂引发相分离制备了聚合物分散液晶膜(PDLC). 利用偶氮液晶的光致相变, 实现了聚合物分散液晶薄膜的光控开关. 实验结果表明, 在PDLC膜内部液晶微球中, 液晶分子呈双极形分布. 其光控温度区间19～36 ℃之间. 以360 nm附近紫外光照射之后, PDLC膜的最大透光率从6%增加到93%. 在相同的工作距离下, 光调制的时间与PDLC膜内部微孔直径相关. 在相同的液晶浓度下, 直径越小, 调制时间越长.     

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。     

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.     

不同醇对聚合物分散液晶光聚合动力学及其电光特性的影响

以丙烯酸-2-乙基己酯(EHA)、二甲基丙烯酸乙二酯(EDMA)/季戊四醇四丙烯酸酯(PETTA)为混合单体、液晶P0616A为液晶相、Irgacure 184为光引发剂,通过UV光引发制备了聚合物分散液晶(PDLCs),研究了不同烷基链长醇,即乙醇(EtOH)、正丁醇(nBA)、正己醇(nHA)、正辛醇(nOA)和正十四醇(nTA)对体系光聚合动力学及其PDLCs液晶相变温度及电光特性的影响.结果表明引入醇分子显著加快了丙烯酸酯/液晶复合体系的光聚合反应速率,提高了单体的最终转化率,其中以正丁醇体系最为明显.随着醇分子烷基链的增长,体系的转化率趋于降低,但依然明显高于不含醇的体系.醇分子的加入降低了PDLCs中液晶相的TNI,且随着醇分子烷基链长的增长,PDLCs液晶相的TNI总体上呈降低的趋势.醇分子的加入增加了PDLCs液晶微区中向列相液晶的含量,而含正丁醇和正十四醇的体系液晶微区中向列相液晶低于其它3个含醇体系.醇分子的加入明显降低了PDLCs的阈值电压和饱和电压以及对比度.结合体系的光聚合速率和单体转化率,正丁醇是改善PDLCs性能的最佳选择.     

聚合物 分散液晶体系的相分离结构对温度依赖性的研究

在不同温度下采用紫外光引发相分离法制备了聚合物分散液晶样品．用光学显微镜及扫描电镜研究了样品的相分离结构．采用对样品施加电压观察其微结构轮廓，或测量液晶微粒相变点的简单方法研究了聚合温度对相分离结果的影响．结果表明，在一定温度范围内，随着温度的增高，液晶微粒的平均尺寸趋于减小，而且形成的液晶微粒也逐渐变纯．作者给出了这些测试结果并进行了讨论．     

预取向液晶单体光聚合反应

通过表面摩擦、施加外电场(或磁场)和应力剪切等手段使液晶单体取向后进行光聚合反应是制备高度取向、高度均匀和高度透明高分子液晶膜的重要方法。它在高分子非线性光学材料、导电商分子材料和光纤涂层等领域中具有广泛的应用前景。     

单体结构对全息聚合物分散液晶光栅稳定性的影响

使用3种不同化学结构的单体材料制备了全息聚合物分散液晶光栅,并从光栅形貌、衍射能力、驱动特性、聚合物热稳定性4个方面评价了光栅的热稳定性.研究发现,含有刚性结构单体材料体系的光栅形貌、衍射能力等方面在200℃的温度下没有明显变化.表明光栅的热稳定性与单体材料的化学结构密切相关,单体材料中含有刚性结构有助于光栅热稳定性的提高.利用热重分析(TGA)对光栅中聚合物材料热分解温度进行了测定,并结合Freeman-Carroll微商法计算出了上述聚合物的分解活化能和分解反应级数.结果发现,含有刚性结构的聚合物材料的热分解温度、分解活化能和分解反应级数都高于柔性链结构材料,进一步验证了材料体系中刚性结构的添加有助于提高光栅的热稳定性.     

聚合物稳定液晶材料研究进展

聚合物稳定液晶材料在显示传感、温度调控、智能材料等方面表现出优异性能,成为液晶材料领域的研究热点.针对向列相液晶、胆甾相液晶、铁电相液晶、蓝相液晶和其他相态液晶,分别介绍了聚合物网络在不同相态液晶中的作用,阐述了不同聚合物稳定液晶材料的特点及光学性能,综述了聚合物稳定液晶材料的研究进展,并指出了聚合物稳定液晶材料面临的...     

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.     

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.     

The effect of the resultant microphase-separated structures of polymer matrices on the electro-optical properties of polymer dispersed liquid crystal films by Iniferter polymerization

Iniferter polymerization was employed to prepare polymer dispersed liquid crystal (PDLC) films and an additional photoinitiator was introduced to induce the phase separation of polymer matrices themselves on the process of preparing the PDLC. The effect of the polymerization kinetics and the resultant microphase-separated structures of polymer matrices on the electro-optical properties of PDLC films were studied. It was found that the bigger length scale of phase separation of polymer matrices induced strong light-scattering resulting in low ON-state transmittance. And faster polymerization kinetic induced higher threshold and saturation voltages.     

Photo-polymerization of liquid crystalline monomer in oriented liquid crystal phase

<正>A new approach to synthesize liquid crystalline polymer with narrow polydispersity index(PDI) was developed.Photopolymerization of 4-cyanophenyl-4'-(6-acryloyloxyhexyloxy)benzoate(RM23) in nematic liquid crystals with macroscopic orientation was studied.The effects of the monomer concentration on the molecular weight and PDI of the resulting polymers were studied through gel permeation chromatography(GPC) and polarized optical microscopy.The low PDI of 1.19 and 1.22 was obtained in the reverse and normal modes,respectively.The PDI and molecular weight increased with monomer concentration.     

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.     

环氧基PDLC的制备及其电光性质

PDLC是一种新型的固态显示器件,具有优良的光电响应性能。我们以环氧交联法制备PDLC膜,考察了不同固化条件、浓度配比对PDLC膜形态结构的影响,讨论了凝胶点和分相机理的关系,进而测量了PDLC膜的光电响应,并对其响应过程提出了新的看法。     

红外光谱结合线阵列检测技术研究聚合物分散液晶膜分子取向

采用偏振红外光谱和变温红外光谱研究聚合物分散液晶膜中液晶分子取向随外加电场及温度的变化.利用线阵列检测技术表征了聚合物与液晶界面处的成分分布.结果表明,线阵列检测技术能够快速而直观地给出成分分布图,通过该成分分布图可以解释PDLC在温度场作用下分子取向的变化.     

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.     

Effects of a chemically modified multiwall carbon nanotubes on electro-optical properties of PDLC films

Polymer dispersed liquid crystal (PDLC) films are fabricated by well-known polymerization-induced phase separation method. In this paper, the dispersion of multi-walled carbon nanotubes (MWCNT) in liquid crystals has been enhanced by chemical modification and we have investigated their effects on the morphology, electro-optical properties and conductivity of the PDLC films. Results indicated that the threshold voltage and the saturation voltage of PDLC films decreased with the increase of the doping concentration of MWCNT or chemically modified MWCNT, because carbon nanotubes can enhance the electric field by reducing the resistivity of the medium and increasing the capacitance of the cells. It can be viewed obviously that the contrast ratio of the PDLC films doped with the chemically modified MWCNT is higher than that of the MWCNT.     

Effect of external electrical field on phase behavior and morphology development of polymer dispersed liquid crystal

Phase diagrams for mixtures of liquid crystal (LC)/monomer with and without an external electrical field applied have been established using polarized light microscope (PLM).The (isotropic + nematic) coexistent phase region and (isotropic + isotropic) phase boundary of LC/monomer mixtures were observed to shift upward to higher temperatures when the external electrical field exists. It was found that the electrical field applied during the cross-linking polymerization has a significant influence on the phase diagrams for the LC/polymer mixtures by rendering the coexistent phase regions shift upward to higher temperatures. The influence of the external electrical field on the processes of the isotropic-isotropic phase separation and liquid crystal ordering in PDLC formation has also been investigated. The results revealed that both the processes could be highly accelerated by the electrical field.