Polyimide photo-alignment layers for inclined homeotropic alignment of liquid crystal molecules

We have succeeded in realizing an inclined homeotropic alignment of liquid crystal (LC) molecules by using photo-aligned films of a polyimide containing azobenzene in the backbone structure. To induce such an LC alignment, a side chain structure was introduced into the backbone structure. The LC pretilt angle, measured from the surface normal, could be controlled up to 1.75° by varying the light exposure in oblique angle irradiation with unpolarized light. Its thermal stability was examined by annealing the LC cell at 100 °C. No change was observed in the pretilt angle even after annealing for 36 h, indicative of its excellent thermal stability. Since photo-alignment has patterning capability, the photo-aligned polyimide film is expected as a promising alignment film for multi-domain vertical alignment mode LC displays.     

添加剂对聚酰亚胺液晶垂直取向剂性能的影响

研究了添加剂对PI取向性能、耐摩擦性、热稳定性以及透光率的影响。用均苯四甲酸二酐(PM-DA),对苯二胺(PDA),4-已氧基联苯酚-3’,5’-二胺基苯甲酸酯(C6-BBDA),制备了三元共聚型PI取向膜,并采用添加剂(封端剂和交联剂)对PI改性。通过调节添加剂的组成制备了4种PI。利用红外光谱仪(FT-IR)、热失重分析仪(TGA)、紫外分光光度计(UV-Vis)、偏光显微镜(POM)和预倾角测试仪对合成的PI进行了结构表征和性能测试。研究发现LC分子在4种PI膜上都获得了均匀的垂直取向;添加交联剂的PI膜具有良好的耐摩擦性,经摩擦强度为600mm摩擦后,仍对LC分子具有垂直取向的能力;加入添加剂的PI膜具有良好的热稳定性,此外,加入添加剂的PI膜仍具有较高的透光率。     

Photo-induced liquid crystal alignment of poly(vinyl cinnamate) and fluorinated polyimide blends

Liquid crystal(LC) alignment properties were mainly affected by surface properties of alignment layers. In our previous work, we prepared poly(vinyl cinnamate) (PVCi) and polyimide blend alignment layer for thermally stable LC alignment. In this work, we utilized fluorinated polyimide for blend alignment layers in order to modify surface properties of alignment layers. For this purpose, polyimides containing fluorine unit were synthesized and used for the blend alignment layers. Fluorine containing diamine, 4,4′-bis[2-(4-aminophenyl)hexafluoropropyl]-diphenyl ether(BDAF), is used for the polyimide synthesis. We prepared the fluorinated polyimide and PVCi blend alignment layers and investigated the effect of fluorine on the LC alignment properties and pretilt angle of LC.     

Effect of the shape of imprinted alignment layer on the molecular orientation of liquid crystal

The molecular alignment of liquid crystals was studied with three different imprinted patterns. The three different shapes of molds (square-, V- and U-shaped) replicated the microstructures with electroplating process was fabricated. Surfaces with three different microgrooved patterns were used as the alignment layer of the liquid crystal cell. The effect of the shape of imprinted alignment layer on the molecular orientation of LC was investigated. Among these patterns, U-shaped groove pattern resulted in a high performance of liquid crystal orientation, pretilt angle and anchoring energy, which are quite comparable to the conventionally rubbed layer. It clearly shows that the molecular orientation of liquid crystals is influenced by the shape of microgrooved patterns.     

单胺添加剂对聚酰亚胺取向材料性能的影响

通过引入单胺添加剂，合成了三类、八种聚酰亚胺取向材料，采用热重分析对它们的热稳定性进行了研究。结果表明，单胺的加入使聚合物的分子量降低，粘度和热稳定性下降。对于不含强极性基团的聚酰亚胺取向材料，适当地加入单胺可增大预倾角；对于含有强极性基团的聚酰亚胺取向材料，单胺的加入对预倾角的影响很小。     

Improved liquid crystal pretilt angles by patterned dual alignment coating structures

The pretilt angles for the optically compensated bend (OCB) mode liquid crystals have been improved using novel patterned dual alignment coating structures in this study. The transition from the splay configuration to the bend configuration can thus be effectively reduced. The dual alignment coating structures consisted of a horizontal alignment polyimide (PI) and a patterned vertical alignment liquid crystal polymer (LCP). Three patterning masks were designed for the photolithography process. The pretilt angles were demonstrated to be increased to 34 degrees for the triangle lattice array-patterned cells. It became 31 degrees for the square lattice array-patterned cells, and 24 degrees for the honeycomb lattice array-patterned cells. The improved pretilt angles were illustrated by the force balance model that can be predicted by the LCP area ratio. The effective control over the pretilt angle could improve the response time to 2 ms when the voltage was ramped up to 5.5 V for the OCB mode liquid crystal devices.     

Thin films of a self-assembling peptide on TiO2 and Au studied by NEXAFS,XPS and IR spectroscopies

EAK16 is a 16 amino acid peptide consisting of an alternation of polar and non-polar pending groups and of positively and negatively charged residues, that makes this material capable of self-assembling, producing an extended ordered structure.Thin films of EAK16 were prepared on TiO₂ and Au surfaces and investigated by surface-sensitive techniques such as XPS (X-ray photoelectron spectroscopy), NEXAFS (near edge X-ray absorption fine structure) and IR spectroscopies.XPS analysis allowed to check the chemical structure of the samples and to determine the film thickness. IR experiments yielded evidence of the β-sheet conformation of the peptide backbone. Polarization dependent NEXAFS measurements allowed estimating the angle between the axis of the peptide backbone and the sample surface.     

液晶种类及工艺条件对预倾角的影响

用均苯四羧酸二酐(PMDA),1,2,3,4-环丁烷四羧酸二酐(CBDA)和4((4-氨基苯基)-二(4-甲氧基苯基)甲基)苯胺共聚制备聚酰亚胺,并用做液晶取向膜。采用正交偏光显微镜和预倾角测试仪分别表征了液晶的取向效果及其预倾角;考察了液晶种类、二胺与二酐比例、摩擦深度、摩擦次数等工艺条件对预倾角的影响。结果表明,不同的液晶对预倾角有较大影响,普通液晶E7获得的预倾角只有3.5°左右,而ZLI-2293可获得4°以上稳定的预倾角,且液晶取向均匀良好。同时,得到了最佳的二胺与二酐配比、摩擦深度和摩擦次数。     

Use of polydimethylsiloxane thin film as vertical liquid crystal alignment layer

The possibility of the use of polydimethylsiloxane to align liquid crystals is studied. The polydimethylsiloxane thin films coated on glass substrates exhibit a very low surface free energy, and are found to be capable of vertical liquid crystal alignment. Comparing to thin films made using a typical polyimide polydimethylsiloxane films possess a more stable surface energetic state. The pretilt angle of the calamitic liquid crystal molecules sandwiched between the silicon elastomer thin films was virtually 90°, and the molecular tilt can be maintained in a wide temperature range. Liquid crystal sandwiched between the silicon-based polymer thin films can operate in the in-plane-switching mode.     

Surface modification of a flexible polyimide film using a reactive fluorinated polymer nanosheet

This paper describes an effective approach to surface modification of a flexible polyimide film using a reactive fluorinated polymer nanosheet. N-(1H,1H-pentadecafluorooctyl)methacrylamide copolymers containing carboxyl group as a reactive moiety form stable monolayer on the water surface and highly ordered reactive polymer nanosheets can be fabricated by the Langmuir-Blodgett technique. This reactive fluorinated polymer nanosheet was utilized to modify the surface properties of polyimide film through its immobilization using thermal treatment. The modification process was studied by X-ray photoelectron spectroscopy (XPS) and modified PI surface was characterized by contact angle measurements and atomic force microscopy (AFM).     

含氟丙烯酸酯核壳乳液的合成与性能

采用三阶段种子半连续乳液聚合,制得了以BA(丙烯酸丁酯)-MMA(甲基丙烯酸甲酯)共聚物为核,BA-MMA-TFEA(甲基丙烯酸三氟乙酯)共聚物为壳的核壳型含氟丙烯酸酯乳液.对乳液聚合过程中单体转化率的变化,特别是乳胶粒子的增长及分布的演变进行了测试和分析,证实了乳胶粒子核壳结构的形成.乳液聚合物膜的性能测试结果表明,与相同含氟单体用量的常规孔液相比,含氟聚合物富集于壳层的核壳形态有利于含氟结构单元在聚合物膜表面的分布,使用少量的含氟单体即可显著降低聚合物膜的表面能,提高其耐水性.     

Homogeneously aligned liquid crystal display on silicon oxynitride thin film using ion beam bombardment

This paper introduces the homogeneously aligned liquid crystal (LC) display using ion beam (IB) bombardment of a new silicon oxynitride (SiON) alignment layer for the first time. The pretilt angle was shown to be a function of the IB incident energy, and possible mechanisms of LC alignment were investigated with physical and chemical methods. An X-ray photoelectron spectroscopy analysis showed that the LC alignment on the IB-bombarded SiON inorganic surface was due to the reformation of Si–O bonds as a major factor. The electro-optical characteristics were comparable to those of rubbed polyimide films.     

Electric force microscopy study of the surface electrostatic property of rubbed polyimide alignment layers

Two polyimides were synthesized for use as alignment layers. The pretilt angles of the liquid crystals, 4-cyano-4′-n-pentylbiphenyl, on the two polyimides were measured by the crystal rotation method. The relative surface atomic concentrations of F/C (%) were measured by X-ray photoelectron spectroscopy. Electric force microscopy was utilized to investigate the surface electrostatic property of the two thin polyimide alignment layers before and after rubbing. All results demonstrate that rubbing causes trifluoromethyl moieties to migrate towards the surface, absorb negative charges and orient along the rubbing direction. Thus, it is proposed that distributions of functional groups on the surface of the polyimide after rubbing are anisotropic and the van der Waals forces between the polar groups and liquid crystal molecules play an important role in the uniform orientation of the liquid crystal molecules.     

Orientational control of liquid crystal molecules by reformed poly(dimethylsiloxane) alignment layer via ion-beam irradiation

We introduce an alternative approach to making a reformed PDMS layer as a pretilt controllable alignment layer, which can be used in the vertical alignment (VA) and twisted nematic (TN) modes, by varying the ion beam (IB) energy. Depending on different the dielectric anisotropy of surfaces, PDMS layers have been demonstrated to align LC molecules homogeneously and homeotropically. The electro-optic characteristics of aligned VA and TN-LCD based on PDMS layer were comparable to those of VA and TN-LCD based on polyimide, showing good potential of PDMS film as an alignment layer.     

PUA木器油墨性能与成膜助剂分子结构的相关性

目的 探究不同成膜助剂分子结构对聚氨酯丙烯酸酯（PUA）木器油墨墨膜性能的影响。方法 以成膜助剂作为研究对象,使用PUA作为连接料,与消泡剂等助剂一起制备木器油墨。研究成膜助剂3-甲氧基-3-甲基-1-丁醇、乙二醇丁醚、丙二醇、二乙二醇丁醚和二丙二醇丁醚对PUA木器油墨性能的影响。采用FTIR研究成膜助剂/连接料复合乳液薄膜的化学结构,并对其硬度、附着力、接触角表面性质进行表征。结果 助剂相对分子质量越小,墨膜硬度、附着力越大。当乙二醇丁醚的质量分数为4%时,硬度最大为3H,附着力为最佳等级0;醚键和羟基的相对含量越多则其硬度、附着力和接触角越大,丙二醇质量分数为4%时接触角最大（95.3°）。结论 选择质量分数为4%的丙二醇作为成膜助剂时,综合性能最佳;选择成膜助剂时应优先考虑相对分子质量小、极性基团相对含量多的助剂。     

Characterization of surface oxide films on titanium and bioactivity

Biological properties of titanium implant depend on its surface oxide film. In the present study, the surface oxide films on titanium were characterized and the relationship between the characterization and bioactivity of titanium was studied. The surface oxide films on titanium were obtained by heat-treatment in different oxidation atmospheres, such as air, oxygen and water vapor. The bioactivity of heat-treated titanium plates was investigated by immersion test in a supersaturated calcium phosphate solution. The surface roughness, energy morphology, chemical composition and crystal structure were used to characterize the titanium surfaces. The characterization was performed using profilometer, scanning electronic microscopy, ssesile drop method, X-ray photoelectron spectroscopy, common Bragg X-ray diffraction and sample tilting X-ray diffraction. Percentage of surface hydroxyl groups was determined by X-ray photoelectron spectroscopy analysis for titanium plates and density of surface hydroxyl groups was measured by chemical method for titanium powders. The results indicated that heat-treatment uniformly roughened the titanium surface and increased surface energy. After heat-treatment the surface titanium oxide was predominantly rutile TiO₂, and crystal planes in the rutile films preferentially orientated in (1 1 0) plane with the highest density of titanium ions. Heat-treatment increased the amount of surface hydroxyl groups on titanium. The different oxidation atmospheres resulted in different percentages of oxygen species in TiO₂, in physisorbed water and acidic hydroxyl groups, and in basic hydroxyl groups on the titanium surfaces. The immersion test in the supersaturated calcium phosphate solution showed that apatite spontaneously formed on to the rutile films. This revealed that rutile could be bioactivated. The analyses for the apatite coatings confirmed that the surface characterization of titanium has strong effect on bioactivity of titanium. The bioactivity of the rutile films on titanium was related not only to their surface basic hydroxyl groups, but also to acidic hydroxyl groups, and surface energy. Heat-treatment endowed titanium with bioactivity by increasing the amount of surface hydroxyl groups on titanium and its surface energy.     

Photo-induced alignment behavior of azobenzene compound in thin film

Photo-induced molecular alignment behavior of spin-coated poly(4,4′-azobenzene pyromellitamic acid) (PAA(azo)) film was investigated by Fourier transform infrared spectroscopy measurement, atomic force microscope and transmission electron microscope observation. As-spun PAA(azo) flm was found to be smooth and uniform with an amorphous structure. Upon irradiation of linearly polarized ultraviolet light, the molecular ordering and crystallization were induced, and the film surface was roughened slightly. The PAA(azo) film converted to poly(4,4′-azobenzene pyromellitimide) (PI(azo)) film with higher ordering and crystallinity by subsequent thermal treatment. The PI(azo) film was useful as an active layer to introduce the molecular alignment of copper phthalocyanine (CuPc).     

偶联剂处理镀镍碳纤维/环氧树脂界面特性

采用硅烷偶联剂KH560对镀镍碳纤维进行偶联处理。通过扫描电镜、 红外光谱、 接触角测量和单丝复合体系多次断裂法测试研究对比偶联处理前后碳纤维的表面形貌、 结构、 润湿性能以及纤维/树脂体系的界面状态和粘结性能。结果显示: 偶联处理后, 镍镀层表面平整, 羟基等表面极性基团增加, 表面涂覆的KH560膜层完整; 镀镍碳纤维/树脂界面的浸润性得到改善; 镀镍碳纤维/环氧树脂的界面处没有气泡产生, 断点两侧的脱粘现象减轻; 单丝饱和断点数由46增加到65; 镀镍碳纤维/环氧树脂的界面剪切强度由(34.87±2.23)MPa提高到(72.51±3.77)MPa。     

Rational Tuning of Molecular Interaction and Energy Level Alignment Enables High‐Performance Organic Photovoltaics

The performance of organic photovoltaics (OPVs) has rapidly improved over the past years. Recent work in material design has primarily focused on developing near‐infrared nonfullerene acceptors with broadening absorption that pair with commercialized donor polymers; in the meanwhile, the influence of the morphology of the blend film and the energy level alignment on the efficiency of charge separation needs to be synthetically considered. Herein, the selection rule of the donor/acceptor blend is demonstrated by rationally considering the molecular interaction and energy level alignment, and highly efficient OPV devices using both‐fluorinated or both‐nonfluorinated donor/acceptor blends are realized. With the enlarged absorption, ideal morphology, and efficient charge transfer, the devices based on the PBDB‐T‐F/Y1‐4F blend and PBDB‐T‐F/Y6 exhibit champion power conversion efficiencies as high as 14.8% and 15.9%, respectively.     

基于1,2,4-三羧基-3-羧甲基环戊烷二酐的可溶性聚酰亚胺垂直取向剂的制备及性能

采用1,2,4-三羧基-3-羧甲基环戊烷二酐（TCA）、4,4’-二氨基二苯甲烷（MDA）及长侧链二胺4-十二烷氧基苯甲酸酯联苯酚-3’,5’-二胺基苯甲酸酯（DBPDA）共聚制备了一系列的聚酰亚胺。并对其溶解性能、透光性能及取向性能进行了测试。结果显示,聚酰亚胺在有机溶剂中可溶,成膜后紫外透光率较高,在波长400 n...