New semiconducting multi-branched conjugated molecules based on π-extended triphenylene and its application to organic field-effect transistor

Triphenylene derivatives are the most well-known representatives of discotic liquid crystals forming columnar mesophases. In this work, the authors report on the design and synthesis of new semiconducting materials, based on a triphenylene core, those are solution processable. These molecules have a good solubility and are applicable to soluble processing for organic field-effect transistor (OFET). Their thermal stabilities and dynamic behaviors are suitable for OFET device fabrication. In comparison with all of previous reported triphenylenes derivatives, these molecules have lower bandgap energies. As far as we know, there are few reports on the application of π-extended triphenylene systems to OFET. The semiconducting properties of these molecules were quite promising for further designs of π-extended triphenylene derivatives.     

New semiconducting multi-branched conjugated molecules based on π-extended triphenylene and its application to organic field-effect transistor

Triphenylene derivatives are the most well-known representatives of discotic liquid crystals forming columnar mesophases. In this work, the authors report on the design and synthesis of new semiconducting materials, based on a triphenylene core, those are solution processable. These molecules have a good solubility and are applicable to soluble processing for organic field-effect transistor (OFET). Their thermal stabilities and dynamic behaviors are suitable for OFET device fabrication. In comparison with all of previous reported triphenylenes derivatives, these molecules have lower bandgap energies. As far as we know, there are few reports on the application of π-extended triphenylene systems to OFET. The semiconducting properties of these molecules were quite promising for further designs of π-extended triphenylene derivatives.     

对称型苯并菲盘状液晶研究进展

盘状液晶是近年来研究的一种新型光电材料,其独特的光电性能显示了巨大的应用前景,本文主要从类型与合成方面介绍了近年来对称型苯并菲盘状液晶的研究进展.     

Alignment change of hexahexylthiotriphenylene in the helical columnar phase by infrared laser irradiation

Alignment change of discotic liquid crystal domains induced by infrared irradiation was investigated for the helical columnar phase of hexahexylthiotriphenylene. A uniform and anisotropic alignment change was observed when a linearly polarized infrared light was irradiated. It was found that the IR laser irradiation leads to a homogeneous planar alignment even in the helical columnar phase which is highly ordered mesophase. The in-plane order parameter of triphenylene ring was estimated to be 0.82 from the dichroic ratio obtained by polarized infrared absorption measurements. The results strongly imply that the infrared irradiation is a possible technique for device fabrication by use of the helical columnar phase which exhibits a high carrire mobility (~ 10^− 1 cm² V^− 1 s^− 1).     

Uniaxial alignment of nanoconfined columnar mesophases

By confining discotic phthalocyanines in a network of crisscrossed nanogrooves, we obtain a uniaxial alignment of the columnar mesophase. The alignment process is based on the anisotropy of interface tension between the mesophase and the nanogrooves' walls. Preferential mesophase alignment results from this nonhomogeneity combined with the anisotropy of the network cell dimensions. A simple model is proposed to explain the experimental observations.     

盘状液晶材料及电导性能研究的最新进展

盘状液晶分子易于形成柱状相结构材料,从而具有较高的电导特性,是理想的电载流子传输材料,可用于制备光电器件。本文主要介绍苯并菲、酞菁、六苯并冠等盘状液晶材料的制备、电导性能的研究以及在器件应用研究中如纳米导线、有机太阳能电池的最新进展。     

Template synthesis of nanophase mesocarbon

Templating techniques are used increasingly to create carbon materials with precisely engineered pore systems. This article presents a new templating technique that achieves simultaneous control of pore structure and molecular (crystal) structure in a single synthesis step. With the use of discotic liquid crystalline precursors, unique carbon structures can be engineered by selecting the size and geometry of the confining spaces and selecting the template material to induce edge-on or face-on orientation of the discotic precursor. Here mesophase pitch is infiltrated by capillary forces into a nanoporous glass followed by slow carbonization and NaOH etching. The resulting porous carbon material exhibits interconnected solid grains about 100 nm in size, a monodisperse pore size of 60 nm, 42% total porosity, and an abundance of edge-plane inner surfaces that reflect the favored edge-on anchoring of the mesophase precursor on glass. This new carbon form is potentially interesting for a number of important applications in which uniform large pores, active-site-rich surfaces, and easy access to interlayer spaces in nanometric grains are advantageous.     

The driving force for homeotropic alignment of a triphenylene derivative in a hexagonal columnar mesophase on single substrates

An interesting discotic triphenylene derivative, 2,7-biscarbethoxy-3,6,10,11-tetrapentyloxytriphenylene, can be homeotropically aligned on a large scale as a film on single substrates, i.e. the film with one side on the substrate and the other side freestanding. The alignment is achieved in a controlled condition close to a thermodynamic equilibrium state in a liquid crystal phase when interactions at the substrate surface are limited. Phase changing properties of this material are also a key factor in the alignment processes. The aligned structures are observed with an optical microscope. Within a single domain a hexagonal lattice of a d-spacing 16.3 Å is confirmed by X-ray diffraction measurement.     

石墨烯纳米复合材料的制备及结构表征

制备了含羟基的三亚苯衍生物,2,3,6,7,10,11-六（10′-羟基癸氧基）三亚苯（HHDTP）。利用核磁共振（1H-NMR）对其结构进行了表征。通过Hummers法制备了氧化石墨（GO）。通过三亚苯基团与石墨烯片层之间强烈的π-π相互作用,在GO还原为石墨烯的过程中将HHDTP与石墨烯复合,得到了一种新型纳米复合...     

Alignment control of columnar liquid crystals with wavelength tunable CO2 laser irradiation

Infrared-induced alignment change with wavelength tunable CO₂ laser irradiation for columnar liquid crystal domains was investigated for a liquid crystalline triphenylene derivative. A uniformly aligned alignment change of domains was observed when a chopped linearly polarized infrared laser light corresponding to the wavelength of the aromatic C-O-C stretching vibration band (9.65 μm) was irradiated. The results strongly imply that the infrared irradiation is a possible technique for device fabrication by use of columnar mesophase as a liquid crystalline semiconductor.     

Wet powder processing of sol-gel derived mesoporous silica-hydroxyapatite hybrid powders

This paper describes a method by which a porous silica coating layer can be obtained on different apatite particles through a simple sol-gel synthesis route. Sol-gel derived powders of hydroxyapatite (HAP) and beta tricalciumphosphate (beta-TCP) were coated with a mesoporous silica using C16TAB (hexadecyltrimethylammonium bromide) as a template in order to induce mesophase formation. Further calcination of the material removes the template from the mesophase and leaves a highly ordered hexagonal arranged mesoporous silica structure with a core of HAP/beta-TCP. The phase purity of the SiO2/apatite composites has been thoroughly investigated by the means of FT-IR, XRD, and solid state 31P MAS NMR. The phase purity of these materials is shown to be dependent on the solubility properties of the used apatites. The hybrid materials are suitable as a multifunctional biomaterial where osteoconductive properties can be combined with drug delivery.     

碳质中间相形成机理研究

碳质中间相是制备高性能炭材料制品的优质前驱体，其产品已在高性能复合材料、超高功率石墨电极和二次锂离子电池用负极材料等方面得到了成功应用。碳质中间相产品的结构复杂、形态各异，造成了生产这些产品涉及的原料和处理过程的多样化。为了分析和预测一定条件下获得的碳质中间相产品的性能，进而确定其具体的用途，需要弄清碳质中间相的形成机理。通过系统地探讨碳质中间相的形成过程，对以往文献中的解释给予了归纳和分析。分析认为传统解释中存在许多不合理的地方，不能对一些现象给予合理的解释；“微域构筑”理论在传统解释的基础上有了很大进步，但由于该理论中引入了实际上并不存在的片层微晶单元而使其存在缺陷；“颗粒基本单元构筑”理论摒弃了以上两种理论中的不合理成分，能够对碳质中间相的形成过程进行很好的解释。此外，对“颗粒基本单元构筑”理论的一些应用也进行了讨论。     

不同形状中间相沥青炭纤维的横断面结构

在场发射扫描电子显微镜（ＦＥ－ＳＥＭ）下观察了圆形、中空、条形和Ｙ－形中间相沥青炭纤维的横断面结构,用流变学理论分析了纺丝过程中几种炭纤维结构的形成,提出中空纤维纺制时沥青流体的最大流速线在喷丝孔中心线的内侧,并根据中空炭纤维横断面的显微照片对此加以证实,用催化缩聚中间相沥青制备的条形炭纤维显示出的特殊弧形对称结构,起因于中间相沥青的流变性质和条形喷丝孔的形状设计,非圆形中间相沥青炭纤维趋向于以线     

同步氢化/热缩聚法制备中间相沥青的工艺研究

系统地研究了在氢化剂量固定情况下,反应温度与时间对同步氢化/热缩聚法所制得的中间相沥青(MP)性质的影响,并制得了可纺MP。研究表明反应时间同为4h时,MP的软化点和不溶分含量随反应温度的提高而升高;偏光结果显示,低温产物为中间相小球和各向同性基质的混合物,高温产物为连续中间相。反应温度同为410℃时,MP软化点和不溶分含量均随反应时间的延长而显著提高,经历了从中间相小球到小球发生融并,最后形成了马赛克织构的中间相。纺丝性能测试表明,反应温度为410或420℃,反应4h制得的中间相沥青,可以熔融纺丝,经氧化和碳化后制得两组碳纤维。     

Microstructure characterization and thermal properties of the waste-styrene-butadiene-rubber (WSBR)-modified petroleum-based mesophase asphalt

In this work, waste-styrene-butadiene-rubber(WSBR)-modified petroleum-based mesophase asphalt was prepared through a co-carbonization process. The influence of contents of WSBR and carbonization temperature on the properties of mesophase asphalt was investigated. The chemical constituents,microstructure and thermal property of the samples were characterized. The results show that using WSBR as modifier can significantly promote the formation of mesophase. When the temperature is constant, the addition of WSBR results in more optically anisotropic crystal structure in the samples, and a better thermal stability. When the content of WSBR is invariable, with increasing temperature, the content of anisotropic structure in mesophase asphalt becomes higher and more uniform. The thermal stability of the samples is the best when WSBR content is 10 wt%.     

Mesophase formation and chemical changes in petroleum pitch during low-temperature heat soaking

A-240 petroleum pitch was used to study the mesophase formation. The mesophase formation of solvent and solvent-acid extracted pitch were controlled in terms of optical texture by adding aromatic hydrocarbon compounds as nucleating agents. It is possible to improve considerably the coking properties that are enhanced by the ring condensation tendency of the precursor. The mesophase yield of the HF-solvent extracted pitches in the presence of 1% anthracene was increased when compared with HF-solvent extracted pitch in the absence of anthracene. In this case, HF acted as a catalyst along with anthracene for ring condensation, similar to AlCl₃ in the aromatic hydrocarbons.     

Liquid crystalline nanowires in porous alumina: geometric confinement versus influence of pore walls

Aligned liquid crystalline nanowires within ordered porous alumina templates show a pronounced texture on a macroscopic scale. We have investigated the influence of the geometric confinement and the nature of the pore walls on the mesophase formation by means of X-ray diffraction. The apparent texture is the result of a complex interplay of the pore geometry, interfacial phenomena, and the thermal history. Pores with a diameter of a few hundred nm guide the mesophase formation more efficiently than those with a diameter below 100 nm.     

Effects of hydrogenation of petroleum pitch on mesophase formation

The effects of hydrogenation of petroleum pitch on mesophase formation have been studied in terms of the hydrogen donor (D _a) and acceptor (A _a) abilities of starting pitch, the temperature dependence of mesophase content, the thermal properties of the resultant mesophase pitches with differential scanning calorimetry (DSC), and ¹³C-NMR spectra of the mesophase pitches in the liquid and solid states. Hydrogenation of petroleum-derived pitch causes a significant increase of (D _a) and a clear shift of the mesophase generation temperature to the hightemperature side. Measurement of the characteristics of molecular size for mesophase pitches using DSC has been successfully accomplished. The increase of D _a due to hydrogenation cause the production of mesophase having a smaller average molecular size and a more homogeneous molecular size distribution. The decrease of molecular size in the mesophase seems to cause the narrowing of the characteristic peak for mesophase around 180 p.p.m. in ¹³C-NMR spectra in the liquid state.     

大直径中间相沥青纤维纺制时的剪切速率

考察了大直径中间相沥青纤维熔纺过程中中间相沥青在喷丝板微孔区内的流动特性及剪切速率。随熔纺温度及挤出流量的增加,中国相沥青在喷丝板微孔区内剪切速率相应增加。熔纺时控制了挤出流量和牵伸速率的良好匹配,获得了丝径均匀的大直径中间相沥青炭单丝。两种中间相沥青在剪切速率和由其纺制获得纤维的离散系数方面的差异,归结为常压与加压齐聚反应后中间相沥青在本性上的差异。     

从煤焦油硬沥青和苯基硅烷制备硅取代聚芳烃中间相的研究

采取软、硬二种沥青与一,二,四苯基硅烷混合物共炭化方式,考察了硅取代聚芳烃中间相的生成。该炭化过程在反应釜中进行,控制实验条件如下:氩气压强1MPa,温度440℃,热裂解时间5h～10h。研究表明:含2%元素硅的初始混合物,不生成硅取代中间相;添加1.0%和0.5%元素硅的硬沥青炭化时明显生成硅取代中间相,但不是单一相。热裂解残留物是硅取代中间相体和均匀分散其中的无硅中间相小球体构成的复合相。