静电纺丝法制备聚丙烯腈/聚苯胺复合纳米纤维及其表征

利用静电纺丝技术,以聚丙烯腈(PAN)和苯胺(ANI)为前驱物,用过硫酸胺(APS)溶液在低温下缓慢氧化聚合,制备了PAN/PANI复合纳米纤维,直径约500 nm.通过扫描电子显微镜(SEM)、红外光谱(FTIR)、X射线衍射(XRD)和激光拉曼(RAMAN)光谱仪等测试手段对材料的形貌和结构进行了表征.探讨了材料制备过程中影响纤维形貌、尺寸、均匀度的因素和PANI含量对复合纤维导电性能的影响,结果表明,PAN浓度、ANI的加入量和电压是影响纤维特性的主要因素;PANI在PAN基体中呈纳米尺寸分布,复合纳米纤维具有良好的导电性能,导电率可达10-2S/cm.     

超疏水导电聚苯胺的界面聚合

采用界面聚合和无模板法相结合的方法, 以具有疏水链的全氟癸二酸(PFSEA)为掺杂剂, 通过调节苯胺单体和FeCl₃氧化剂的浓度实现了聚苯胺三维微/纳米结构形貌和尺寸的可控制备. 扫描电子显微镜测量结果显示, 聚苯胺是由一维纳米纤维自组装形成的三维微球结构; 红外吸收光谱和紫外-可见吸收光谱结果表明, 聚苯胺微球为掺杂态. 室温下, 该微/纳米结构聚苯胺微球的电导率为 9.6×10^-3 S/cm, 表面水接触角为161.4°, 表现出半导体特性和超疏水性.     

Formation of polyaniline nanofibers: a morphological study

Polyaniline (PANI) powders were prepared by solution precipitation, rapid mixing polymerization, and interfacial polymerization to find the key factors that influence the formation and growth of PANI nanofibers. In chemical oxidative polymerization of aniline, the morphology of the product is mainly determined by aniline concentration. In the case of lower aniline concentration, PANI nanofibers were formed and can be preserved and collected as final product, while in the case of higher aniline concentration, larger sized PANI particles or agglomerates were obtained owing to the growth of the nanofibers. Without participation of the oxidizing step, solid PANI samples with compact structures and dissimilar morphologies were achieved by random accumulation of PANI molecules.     

乳液聚合中聚苯胺膜形成的动力学研究

以(NH4)2S2O8(APS)为氧化剂,十二烷基苯磺酸(DBSA)同时为乳化剂和掺杂剂,采用乳液聚合方法制备聚苯胺膜(PANIfilm),用石英晶体微天平(QCM)实时监测聚苯胺膜的形成过程,并对其动力学过程进行研究.结果表明,聚苯胺成膜反应对APS是0.5级,对苯胺是1级,聚苯胺膜增长速率随温度的升高而增加,而聚苯胺膜的最终沉积量却减小,表观活化能Ea=41.15kJ/mol,与均相溶液聚合成膜法的结果相近;随着DBSA浓度的增加,聚苯胺膜增长速率减小,而最终的沉积量增大.     

Graphene oxide‐induced polymerization and crystallization to produce highly conductive polyaniline/graphene oxide composite

Graphene oxide (GO)–polyaniline (PANI) composite is synthesized by in situ polymerization of aniline in the presence of GO as oxidant, resulting in highly crystalline and conductive composite. Fourier transform infrared spectrum confirms aniline polymerization in the presence of GO without using conventional oxidants. Scanning electron microscopic images show the formation of PANI nanofibers attached to GO sheets. X‐ray diffraction (XRD) patterns indicate the presence of highly crystalline PANI. The sharp peaks in XRD pattern suggest GO sheets not only play an important role in the polymerization of aniline but also in inducing highly crystalline phase of PANI in the final composite. Electrical conductivity of doped GO–PANI composite is 582.73 S m^?1, compared with 20.3 S m^?1 for GO–PANI obtained by ammonium persulfate assisted polymerization. The higher conductivity appears to be the result of higher crystallinity and/or chemical grafting of PANI to GO, which creates common conjugated paths between GO and PANI. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1545–1554     

Preparation and characterization of polyaniline-containing Na-AlMCM-41 as composite material with semiconductor behavior

Composite material formed from a mesoporous aluminosilicate, Na-AlMCM-41, with conducting polyaniline (PANI) has been synthesized by an in situ polymerization technique. Studies of aniline adsorption over mesoporous Na-AlMCM-41 synthesized in our laboratory allowed us to find the modes in which aniline interacts with the active sites of Na-AlMCM-41. In order to obtain the best reaction conditions to polymerize aniline onto Na-AlMCM-41, aniline was first polymerized to produce pure PANI. Hence, the oxidative in situ polymerization was carried out by two procedures, differing in the polymerization time and in static or stirring conditions. Studies of infrared spectroscopy and UV-vis spectroscopy indicated that higher polymerization time and static conditions allowed us to obtain mainly polyaniline in emeraldine form on the host. The N(2) isotherm of the polyaniline/Na-AlMCM-41 composite (PANI/MCM) indicated that the shape was similar to that of MCM, but the shift to saturation transition to lower partial pressure shows that the channels are occupied by PANI and they are now narrowed. The thermal properties of PANI, Na-AlMCM-41, and composite were investigated by TGA analyses and we found that the polymer shows higher thermal stability when it is forming the composite. Scanning electron microscopy indicated that PANI is not on the outer surface of the host. Conductivity studies show that PANI/Na-AlMCM-41 exhibits semiconductor behavior at room temperature and its conductivity was 7.0 x 10(-5) S/cm, smaller than that of pure polyaniline. PANI/Na-AlMCM-41 conductivity shows an increase as temperature increases. Magnetic measurements at room temperature confirmed that the composite has paramagnetic behavior; at lower temperatures the composite became diamagnetic.     

Exploration on the microwave‐assisted synthesis and formation mechanism of polyaniline nanostructures synthesized in different hydrochloric acid concentrations

Under microwave‐assisted synthesis, polyaniline (PANI) products with multiple nanostructures were synthesized by the oxidative polymerization of aniline and ammonium peroxodisulfate in the different concentrations of hydrochloric acid solutions. The structural analysis of PANI using FTIR, UV, and XPS indicated that phenazine‐like oligomers were produced in acid‐free and low acidic systems. Moreover, long linear PANI chains were obtained in the presence of highly acidic solutions. The morphology of PANI observed by SEM and TEM showed that nanoscale structures, including stacked sheets, nanotubes, branched nanofibers, and uniform nanofibers, occurred respectively in acid‐free solution, low acidity, medium and high acidity systems, effectively regulating by acidity. The formation mechanism of PANI nanostructures was explored here. The sheets were formed by the oligomers containing flat phenazine rings that can be stacked together with strong π–π interactions. Furthermore, nanotubes were fabricated by the self‐curling of thin sheets consisted of phenazine‐like oligomers with numerous linear units in the chains. The nanofibers are supposed to form by the linear PANI chains and the secondary growth during aniline polymerization caused the branch formation on the nanofibers. All results indicate that acidity, rather than microwave assistance, is the critical factor that determines the polymerization mechanism and the final nanostructure. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3357–3369     

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.     

Antioxidant activity of polyaniline nanofibers

Well-confined uniform polyaniline (PANI) nanofibers were synthesized by using photo-assisted chemical oxidative polymer- ization of aniline in the presence of different dopant acids,and the radical scavenging ability of the produced PANI nanofibers was determined by the DPPH assay.It was found that the antioxidant activity of PANI nanofibers was higher than conventional PANI, and increased with decreasing of averaged diameter of the nanofibers.The enhanced antioxidant activity was concerned with increased surface area of PANI nanofibers.     

A comparative study on the viscoelasticity and morphology of polyaniline films galvanostatically grown on bare and 4-aminothiophenol-modified gold electrodes using an electrochemical quartz crystal impedance system and SEM.

The equivalent-circuit parameters of the 9-MHz piezoelectric quartz crystal (PQC) resonance were measured in situ during the galvanostatic polymerization of aniline on 4-aminothiophenol(4-ATP)-modified and bare Au electrodes for ca. 2000 s, respectively. Two polymerization media, 0.100 mol L-1 aniline in 1.0 mol L-1 H2SO4 and in 2.0 mol L-1 HClO4 aqueous solutions, and two values of the current density, 12 and 36 microA cm-2, were used. At identical levels of the resonant frequency shifts in the solutions, obviously greater increases in the motional resistance (R1) were found after aniline polymerization on bare Au electrodes, though the absolute values of delta f0/delta R1 were all large; also, the resonant frequency shifts in air (delta f0g) were considerably smaller for PANI films grown on bare Au electrodes. It is thus concluded that, under identical polymerization conditions, (1) the PANI film grown on a bare gold electrode is rougher, less compact, and can entrap solution more notably; (2) the deposition efficiency of PANI is higher on a 4-ATP-modified Au electrode, owing to a significantly greater observed "dry" frequency shift, and thus a greater "net" mass value of the polyaniline backbone. SEM observations have confirmed that PANI films on 4-ATP-modified Au electrodes were smoother and more compact than those grown on bare Au ones under identical polymerization conditions. In addition, a technique of simultaneous measurements of the electroacoustic admittance of the PQC resonance and the electrochemical impedance was used to monitor the adsorption of 4-ATP onto a PQC gold electrode.     

浸润性可调的导电聚苯胺/聚丙烯腈同轴纳米纤维

聚苯胺(PANI)因其具有可调的导电性、优异的化学稳定性、简单的制备方法等特点, 在化学电源、抗静电涂层、电磁屏蔽材料、抗腐蚀、传感器等领域具有广泛的应用前景[^1~4]. 由于聚苯胺的刚性分子链使得聚苯胺几乎不溶不熔, 难以加工应用, 因此, 将导电聚合物直接制成纳米纤维一直是合成纤维界所希望的目标之一. 此外, 由于材料尺度的减小, 使纳米材料的表面与界面性质,尤其是表面浸润性变得更为突出.浸润性是固体表面的重要特征之一, 它主要由表面的化学组成和微观结构共同决定^[5,6]. 可调的浸润性在超疏水材料、药物传输、仿生材料和微流体等领域具有重要的应用价值^[7~10] , 引起人们广泛关注.     

Effect of methanol on morphology of polyaniline

Constant potential method is used to synthesize polyaniline (PANI) nanofibers in a solution containing methanol. According to shaping theory, the reasons about forming polyaniline nanofibers were suggested. The effects of the synthesis parameters, such as monomer concentration, methanol concentration, HCl concentration, electrode potential, polymerization time, and reaction temperature on the morphology of the PANI films have been investigated. Scanning electron microscopy results was used to characterize the morphology of PANI nanofibers. Both UV-vis absorption spectra and FTIR spectra indicate that there exists interaction between methanol molecules and polyaniline chains.     

A composite polyaniline/graphene–coated polyamide6 nanofiber mat for electrochemical applications

In this study, polyamide6 (PA6) nanofiber mats were fabricated through the electrospinning process. The nanofibers were coated by polyaniline (PANI) using the in situ polymerization of aniline in the presence of graphene oxide. The composite of the PANI/graphene oxide–coated nanofiber mat was treated with hydrazine monohydrate to reduce graphene oxide to graphene, and this was followed by the reoxidation of PANI. Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), wide angle X‐ray diffraction (WAXD), thermal gravimetric analysis (TGA), tensile strength tests, electrical conductivity measurements, cyclic voltammetry (CV), and charge/discharge measurements were conducted on the composite PA6/graphene nanofiber mats. It was found that the surface of the PA6 nanofibers was coated uniformly with the granular PANI and graphene oxide. Besides, the composite nanofibers showed good tensile and thermal properties. Their electrical conductivity and specific capacitance, when used as a separator in the cell, were 1.02 × 10^?4 S/cm and 423.28 F/g, respectively. Therefore, the composite PANI/reduced graphene oxide–coated PA6 nanofiber mats could be regarded as suitable candidates for application in energy storage devices.     

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     

聚苯胺/纳米二氧化锰复合材料Ⅰ.原位氧化合成制备

用固相合成法制备了纳米二氧化锰(nm-MnO2),并通过原位聚合法制备了聚苯胺／纳米二氧化锰复合材料。研究结果表明：在苯胺／nm-MnO2的盐酸反应体系中,nm-MnO2可以使苯胺氧化聚合。在一定的nm-MnO2用量下,聚苯胺的产率随苯胺添加量的增加而下降,nm-MnO2在产物中的含量也随之下降,且含量很低。在苯胺：／nm-MnO2／过硫酸铵的反应体系中,研究了Nm-MnO2通过两种不同的加料方式原位制备PA-NI／nm-MnO2复合材料的合成条件。第一种方式为nm-MnO2和过硫酸铵同时与苯胺混合,一起参与苯胺的氧化聚合。第二种方法是先将过硫酸铵和苯胺混合,3min后再将nm-MnO2加入反应体系中。研究表明：第一种加料方式得到的队NI／nm-MnO2中nm-MnO2的含量很低;第二种加料方式可以得到高nm-MnO2含量(w=0．14-0．73)的产物,其电导率约10^-4S／cm。     

手性聚苯胺纳米纤维的电化学制备

采用恒电位电聚合法制备了樟脑磺酸(CSA)掺杂的旋光异构性聚苯胺(PANI)纳米纤维. 用扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 紫外-可见吸收光谱(UV-Vis)和圆二色光谱(CD)对PANI纳米纤维的形貌和光学性质进行表征, 结合电聚合溶液胶束平均粒径和ζ电位的测定, 研究了具有旋光异构性PANI纳米纤维的形成机理和具有增强旋光异构性的原因. 所制备的PANI纳米纤维具有无双螺旋结构, 其形貌不随着苯胺浓度的改变而变化. 不同手性樟脑磺酸掺杂制备的PANI纳米纤维具有镜像对称的旋光异构性, 且具有较高的椭圆偏振率. 这种手性PANI纳米纤维的颜色和旋光性均可通过化学掺杂/去掺杂或电化学掺杂改变氧化还原态而呈现可逆变化.     

Fabrication and electrochemical instrumentation of redox‐active nanofiber mat for polyaniline incorporated with poly(imide sulfonate)

In this study, we demonstrate the fabrication of an electrochemically active nanofiber mat that is a composite of high‐performance poly(imide sulfonate) (PIS) and polyaniline (PANI). First, a nonconductive nanofiber mat comprising nanofibers having diameters of ca. 300 nm was fabricated by the electrospinning of ionomeric PIS in N,N‐dimethylformamide (DMF). Then, the nanofibers were modified using PANI, which was synthesized by the oxidative polymerization of aniline, yielding an electrochemically active nanofiber mat having a diameter of ca. 350 nm. It was confirmed that PANI was successfully incorporated onto the PIS nanofiber mats by X‐ray photoelectron spectroscopy. Subsequently, we conducted electrochemical measurements of the PANI‐modified nanofiber mats using a tailor‐made attachment in which the working electrode gently comes in contact with the nanofiber mat surface. This attachment was observed to be widely useful in the cyclic voltammetry measurements related to redox‐active nanofibers. These observations are expected to contribute to the advancements in application development of the electrochemically active nanofiber mats.     

纳米纤维聚苯胺膜在不锈钢电极表面的生长过程

研究了脉冲电流法(PGM)聚合苯胺时, 纳米纤维聚苯胺(PANI)膜在不锈钢(SS)电极表面的生长过程. 用计时电位法和扫描电子显微镜(SEM)表征了聚苯胺生长过程的电化学特征和微观形貌; 并通过循环伏安(CV)法研究了苯胺的聚合速率. 结果表明, 聚苯胺的生长经历了两个阶段, 首先是在裸不锈钢电极表面上形成颗粒状聚苯胺, 此时聚合电位约为1.10 V, 经历了30 s后, 电极表面被一层颗粒状聚苯胺膜所覆盖; 在此基础上, 聚苯胺以纳米纤维状结构继续生长, 当颗粒状聚苯胺被纳米纤维状聚苯胺膜完全覆盖时, 聚合电位降至0.75 V左右并保持稳定.     

氯化铁氧化掺杂的聚苯胺纳米纤维团簇

没有外加质子酸的条件下,以氯化铁为氧化剂和掺杂剂,在界面体系中由苯胺(An)采用“无模板”的方法成功地制备了电导率为10-2～10-1S/cm的聚苯胺纳米纤维(d=20～30nm).实验证明FeCl3同时起到氧化剂和掺杂剂的双重作用,从而进一步简化了导电聚苯胺纳米纤维的合成条件.与使用过硫酸铵为氧化剂的传统聚合方法相比,FeCl3较小的氧化/还原电位使产物具有较小的直径和较高的结晶性.同时发现聚苯胺的形貌和电导率均与[FeCl3]/[An]的比例有关.FTIR,UV-Vis,XRD结构表征证实所得的聚苯胺纳米纤维为掺杂态.     

Fabricating and Tailoring Polyaniline (PANI) Nanofibers with High Aspect Ratio in a Low‐Acid Environment in a Magnetic Field

In a 0.010 m HCl solution, we successfully transformed irregular polyaniline (PANI) agglomerates into uniform PANI nanofibers with a diameter of 46–145 nm and a characteristic length on the order of several microns by the addition of superparamagnetic Fe₃O₄ microspheres in a magnetic field. The PANI morphological evolution showed that the PANI nanofibers stemmed from the PANI coating shell synthesized on the surface of the Fe₃O₄ microsphere chains. It was found that the magnetic field could optimize the PANI nanofibers with a narrow diameter size distribution, and effectively suppressed secondary growth. When compared with other microspheres (like silica and polystyrene), only the use of superparamagnetic Fe₃O₄ microspheres resulted in the appearance of PANI nanofibers. Attempts to form these high‐quality PANI nanofibers in other concentrations of HCl solution were unsuccessful. This deficiency was largely attributed to the inappropriate quantity of aniline cations.