Template‐Assisted Synthesis of Self‐Doped Polyaniline: Morphological Effects of Templates on the Conductivity

Self‐doped sulfonated polyaniline (PSA) has been synthesized on the surface of micellar nanoparticles made from positively charged surfactants by biocatalysis. The conformation forced by the electrostatic charge interactions between the positively charged micelle and the negatively charged PSA increases the conductivity of the PSA by three orders of magnitude. The pure PSA recovered from ion exchange, however, shows quite similar electrical properties compared with sulfonated polyanilines reported earlier. The increased conductivity of PSA complexes is as a result of the increased charge carrier concentration caused by a certain conformational locking.

     

聚苯胺/碳化钨导电复合材料的合成

以苯胺和过硫酸胺为原料,采用原位聚合方法合成了聚苯胺/碳化钨(PANI/WC)导电复合材料。研究了反应体系中碳化钨的含量对复合材料电导率的影响,确定了较佳的聚合条件,并且通过FT-IR、XRD、XPS和DSC-TGA等手段对复合材料的结构和性能进行了表征和分析。结果表明:碳化钨(WC)的加入提高了聚苯胺的电子导电性能,复合材料中聚苯胺组分为无定型,WC的晶型在反应前后并未发生变化,复合材料的热稳定性好并且质子化程度更高。     

Synthesis,characterization, and morphology of p‐toluene sulfonic acid‐doped polyaniline: A material for humidity sensing application

Polyaniline (PANI) doped with p‐toluene sulfonic acid was synthesized by chemical polymerization method using (NH₄)₂S₂O₈ as an oxidizing agent. This is a single step polymerization process for the direct synthesis of the conducting emeraldine salt (ES) phase, without the need of doping, dedoping, and redoping of the polymer. Presence of a free carrier tail at higher wavelength, characteristic of extended coil conformation along with a sharp polaronic peak is observed in the UV–vis spectrum of doped PANI in m‐cresol solvent. FT‐IR studies show the characteristic peaks of ES phase along with a sharp peak at 1120 cm^?1 representing vibration band of the dopant ion. Clumps of small fibers resulting in a sponge‐like structure was observed under scanning electron microscope. Thermal studies revealed a three‐step decomposition pattern. Conductivity is found to increase with an increase in the temperature showing “thermal activation behavior.” Decrease in resistance with increasing humidity is observed in a broad range of humidity. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2161–2169, 2005     

聚苯胺/聚合物导电材料研究进展

从制备方法着手综述了近年来聚苯胺/聚合物导电材料研制开发的最新成果，并简介了聚苯胺/聚合物导电材料的应用情况。     

聚苯胺电极的电导率

采用化学氧化聚合法制备聚苯胺(PANI)。利用四探针技术和电流-电压方法对PANI的电导率进行表征测试。基于电子-空穴导电机理和经典电流密度表达式,建立了PANI的有效导电数学模型,该模型可描述为电流密度、电压、温度的函数。对模型的图形分析表明,得到的电流-电压规律与PANI的实验结果一致。对电流密度与温度的关系分析得到的电导率随温度的变化规律与实验现象相符。结果表明:PANI有机半导体主要以耦合电流为主,电流强度随电压(温度)的增加呈现先增大后减小的趋势;低温时,PANI的导电性较好。     

化学聚合法制备电容器用聚苯胺

采用化学聚合法制备电容器用聚苯胺,研究了不同的掺杂剂对聚苯胺(Pan)电导率的影响,并利用TGA、FT-IR等分析手段对聚苯胺的热老化性质进行研究,研究了乳液法产物的二次掺杂现象,并把萃取液涂布于铝箔表面制成固体电容器,结果表明这种聚苯胺应用于固体电容器是可行的。     

凝胶型聚合物电解质的电导率与温度的关系

凝胶型聚合物电解质的电导率与温度的关系孙晓光，林云青，齐力，景遐斌，王佛松（中国科学院长春应用化学研究所长春１３００２２）关键词凝胶电解质，离子电导率，活化能无定形聚合物电解质电导与温度的依赖关系一般可用Ｖｏｇｅｌ－Ｔａｍｍａｎ－Ｆｕｌｃｈｅｒｃ（Ｖ...     

聚苯胺复合导电薄膜的制备及性能

聚苯胺;现场化学氧化聚合;掺杂;可溶性;导电性     

磁场作用下原位聚合制备聚苯胺/纳米ZnO复合材料

首先用硅烷偶联剂(KH550)对所制备粒径在100 nm以下的纳米ZnO进行表面修饰(M-ZnO), 然后在弱磁场(0.4 T)下乙醇/水/十二烷基苯磺酸(DBSA)体系中原位聚合分别制备了重均分子量达3×10⁴的聚苯胺(PANI)及聚苯胺/纳米ZnO复合材料. 红外分析表明纳米ZnO的加入使聚苯胺的特征峰向低波数方向移动|溶解性测试表明聚苯胺及其复合材料在氯仿和N-甲基吡咯烷酮中均有较高的溶解度(高于80%)|X-射线衍射表明磁场能有效地改善聚苯胺主链的规整性, 使聚苯胺分子链有更好离域的π电子体系|M-ZnO的引入显著地提高了PANI的电导率(可达220 S/m), 同时具有较好的透光性(80%)|这表明PANI/纳米ZnO复合材料在柔性光电器件领域具有潜在的应用价值.     

Debye Temperature Dependent Lattice Thermal Conductivity of Silicon

The temperature dependence of the Debye temperature θ_D(T) was applied to analyze the lattice thermal conductivity of Si between 2 and 300 K. The analysis of experimental data in terms of the Dubey model of the two modes of conduction has been carried out by combining the relaxation time for phonon-phonon scattering, point defect scattering and boundary scattering. The relative importance of the contribution of each mode was examined by estimating their percentage contribution to the phonon conductivity. Agreement between theory and experiment is achieved over the whole temperature range of study. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and characterization of C60/polyaniline composites from interfacial polymerization

C₆₀/polyaniline (PANI) nanocomposites have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in the presence of C₆₀ by using an interfacial reaction. When compared with the pure PANI nanofibers from the similar process, the diameter of the obtained C₆₀/PANI nanofibers was increased because of the encapsulation of C₆₀ into PANI during aniline polymerization, which resulted from the charge‐transfer interactions between C₆₀ and aniline fragment in PANI. In addition, the resulting C₆₀/PANI nanocomposites synthesized from the low initial C₆₀/aniline molar ratio (less than 1:25) showed the homogenous morphology composed of fiber network structures, which has an electrical conductivity as high as 1.1 × 10^?4 S/cm. However, the C₆₀/PANI nanocomposites from the higher initial C₆₀/aniline molar ratio (more than 1:15) showed the nonuniformly distributed morphology, and the electrical conductivity was decreased to 3.5 × 10^?5 S/cm. Moreover, the C₆₀/PANI nanocomposites from the interfacial reaction showed a higher value of electrical conductivity than the mechanically mixed C₆₀/PANI blends with the same C₆₀ content, because of the more evenly distributed microstructures. FTIR, UV–vis, and CV data confirmed the presence of C₆₀ and the significant charge‐transfer interactions in the resultant nanocomposites, which was responsible for the morphology development of the C₆₀/PANI and the variation of the electrical conductivity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis and Characterization of Conducting Polyaniline Doped with Polymeric Acids

Conducting polyaniline doped with polymeric acids was synthesized by a in situ chemical polymerization method. The synthesized polymers were characterized by using UV‐Visible, FT‐IR spectroscopy and SEM analysis. Thermal stability of these polymers was evaluated by using TGA/DSC analysis. Among the three polymeric acids used for doping purpose, poly(vinyl sulphonic acid) doped polyaniline is found to be more conducting than those doped with other acids. From the temperature dependent conductivity measurements, an increase in conductivity with increase in temperature was observed.     

原位聚合沉积聚苯胺薄膜及其电致变色性能

采用原位聚合的方法,以水溶性高分子聚乙烯吡咯烷酮(PVP)为空间稳定剂,直接在玻璃基体表面聚合沉积导电聚苯胺(PANI)薄膜。用扫描电镜(SEM)、紫外可见光谱(UV-Vis)、四探针电导率测试仪和热重分析仪(TG)对聚苯胺膜结构及性能进行了表征。采用循环伏安法测试了薄膜的电致变色性。结果表明:盐酸掺杂聚苯胺薄膜呈翠绿色,薄膜厚115 nm,表面电导率为4.6×10-3S/cm。电致变色实验中聚苯胺电极电位在-6~ 6 V循环变化时,薄膜颜色在黄绿和蓝绿间可逆变化。电致变色前后聚苯胺薄膜的紫外可见吸收光谱表明,随着电极电位的降低,极化子峰发生红移,说明聚苯胺分子链中醌式结构单元被还原,聚苯胺薄膜质子化程度提高。     

Synthesis of PANI and Study of Morphology in the Process of Polymerization

The polyaniline micro/nanostructure was prepared by a self‐assembly process with molybdic acid as dopants in the presence of ammonium persulfate as the oxidant. It was found that the morphology of PANI micro/nanostructure was affected by the concentration of the dopant, that is, the morphology of PANI changed from nanofibers to co‐existence of nanofibers and microspheres as the molar ratio of molybdic acid to aniline varied from 0.01 to 1.5. Under the same condition it was also found that the conductivity value of PANI enhanced from 4.58×10^?3 S·cm^?1 to 3.8×10^?1 S·cm^?1. The structure of PANI was characterized by FTIR and XRD which confirmed the presence of the molybdic acid in the PANI. The electrochemical characteristics of the PANI nanofibers were investigated by means of cyclic voltammetry. The morphology of PANI in the process of polymerization was characterized by SEM. It was found that when the molar ratio of molybdic acid to aniline was 0.3, the morphology of PANI was co‐existence of nanofibers and microspheres and the formation of microspheres was ahead of the nanofibers.     

Thermal conductivity enhancement of MWNTs on the PANI/tetradecanol form-stable PCM

We prepared PANI/tetradecanol/MWNTs composites via in-situ polymerization. DSC results indicated that the composites are good form-stable phase change materials (PCMs) with large phase change enthalpy of 115 J g⁻¹. The MWNTs were randomly dispersed in the composites and significantly enhanced the thermal conductivity of the PCMs from 0.33 to 0.43 W m⁻¹ K⁻¹. The form-stable PCMs won’t liquefy even it is heated at 80°C, so that the MWNTs were fixed in the composite and the phase separation of the MWNTs from PANI/tetradecanol/MWNTs composites won’t occur.     

Temperature Dependence of the Electrical Conductivity of Cyclodiphosph(V)azane Derivative and Its Copper (II) Complex

Correlation of the current-voltage and temperature dependence of the electrical conductivity with the molecular structure data including infrared and ultraviolet spectra of ligand [2,2,4,4-tetrachloro-1,3-diphenyl-2,4-bi(5-imino-4-cyano-3-methylthiopyazo-1-yl-methylcarbodi-thioate)cyclodiphosph(V)zane and its copper complex have been investigated. The result of the electrical conductivity, energy gaps obtained from electrical conductivity in the solid state was consistent with those of semiconductor materials.     

温度,压力对多省并醌类聚合物导电性能的影响

以氯化锌为催化剂，利用多环芳烃蒽，芘等的不同酸酐如１，２，４，５－均苯四甲酸二酐，四氯苯酐等，在３０６℃逐步聚合得到多省并醌类聚合物，仔细纯化后在不同温度，压力下对其他电导率进行了测量，研究了温度，压力对其电导率的影响。     

Temperature Dependence of the Viscosity and Conductivity of Mildly Functionalized and Non‐Functionalized [Tf2N]− Ionic Liquids

A series of bis(trifluoromethylsulfonyl)imide ionic liquids (ILs) with classical as well as mildly functionalized cations was prepared and their viscosities and conductivities were determined as a function of the temperature. Both were analyzed with respect to Arrhenius, Litovitz and Vogel–Fulcher–Tammann (VFT) behaviors, as well as in the context of their molecular volume (V_m). Their viscosity and conductivity are highly correlated with V_m/T or related expressions (R²≥0.94). With the knowledge of V_m of new cations, these correlations allow the temperature‐dependent prediction of the viscosity and conductivity of hitherto unknown, non‐ or mildly functionalized ILs with low error bars (0.05 and 0.04 log units, respectively). The influence of the cation structure and mild functionalization on the physical properties was studied with systematically altered cations, in which V_m remained similar. The T_o parameter obtained from the VFT fits was compared to the experimental glass temperature (T_g) and the T_g/T_o ratio for each IL was calculated using both experimental values and Angell’s relationship. With Walden plots we investigated the IL ionicity and interpreted it in relation to the cation effects on the physical IL properties. We checked the validity of these V_m/T relations by also including the recently published variable temperature viscosity and conductivity data of the [Al(OR^F)₄]^? ILs with R^F=C(H)(CF₃)₂ (error bars for the prediction: 0.09 and 0.10 log units, respectively).     

Enhanced Conductivity of Polyaniline by Conjugated Crosslinking

A novel crosslinked conductive polyaniline (PANI) was prepared by chemically copolymerizing aniline (An) and p‐phenylenediamine (PPDA) with triphenylamine (TPA) as crosslinker, using ammonium peroxydisulfate (APS) as an oxidant. The effects of different preparation conditions on the electrical conductivity of polymers were systematically investigated by adjusting acid kinds, concentration, the ratio of APS/An, the mounts of TPA and PPDA. The crosslinked PANI displayed a conductivity increase of up to 25% compared with the linear one. Their structures were characterized by Fourier‐transformed infrared spectroscopy and X‐ray photoelectron spectroscopy, and the electrical conductivity was also tested by a typical four‐point probe (RTS‐8) technique.

     

高电导率的a—SiHY合金的低温电导特性

用射央求地在硅单晶衬底上沉积出电导率高达６０Ｓ／ｃｍ的ａ－ＳｉＨＹ合金薄膜。在２０－３００Ｋ，对于钇含量高的样品，其电导仍是热激活的。ｌｇσ与１／Ｔ的关系曲线能够被拟合成斜率不同的两条直线，直线的斜率和两直线间拐点所地 温度依赖于膜中钇的含量。但对钇含量低的薄膜，电导对温度的依赖关系度为σ∝ｅｘｐ（－１／Ｔ＾１／４）。结果表明，这些钇含量不同的样品在没的温度范围内具有不同的导电机制。