Quantitative characterization of polyaniline films using Raman spectroscopy: II. Effects of self-doping in sulfonated polyaniline

Partially sulfonated polyaniline (SPANI) prepared by electropolymerization was studied using Raman spectroscopy (RS). The sulfonated substituent is known to induce a self-doping phenomenon, which allows conduction in SPANI in a larger pH range than in PANI. RS allows, to describe and discuss the modifications related to self-doping. It is shown that the charges organization (polaron lattice or bipolaron) on the chain is modified. Self-doping has an effect upon the rings nature, which presents a more oxidized character. The main SPANI characteristics: mean conductivity and high effect of protection against corrosion are explained, thanks to Raman results.     

Optical,electrical, and electrochemical properties of graphene based water soluble polyaniline composites

Polyaniline (PANI) is one of the most common polymers known for its conducting properties. However, poor water solubility limits its applications. In this work, PANI has been functionalized with sulfonic acid groups to produce sulfonated PANI (SPANI) offering excellent solubility in water. To compensate for the decrease of electrical conductivity due to functionalization, SPANI was combined with reduced graphene oxide (RGO) to form SPANI/RGO composites with interesting optical, thermal, and electrical properties. The composites have been characterized using X‐ray diffraction (XRD), field emission scanning electron microscopy, UV–vis absorption spectroscopy, Raman spectroscopy, Fourier‐transform infrared spectroscopy, X‐ray photoelectron spectroscopy, thermogravimetric analysis, cyclic voltammetry, and four probe electrical conductivity measurement. The SPANI/RGO composites show increased thermal stability, reduced optical band gap and improved electrochemical properties compared with the pure polymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42766.     

A facile synthesis of a novel optoelectric material: a nanocomposite of SWCNT/ZnO nanostructures embedded in sulfonated polyaniline

Functionalized single-walled carbon nanotubes (f-SWCNTs) hybridized with freshly prepared zinc oxide (ZnO) nanocrystals have been found to be good luminescent material with tuned emission properties. A three-phase nanocomposite of sulfonated polyaniline embedded with such SWCNT/ZnO nanostructures has been prepared by a simple solution mixing chemical process and characterized by using high-resolution transmission electron microscopy, X-ray diffractometry, Raman spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The study of UV-visible absorption and photoluminescence spectroscopies reveal that the ternary polymer nanocomposite is a luminescent material with enhanced emission intensity. Also an increase in DC conductivity indicates that the nanocomposite is also a good conductive material, satisfying Mott’s variable range hopping model for a two-dimensional conduction. Such a three-phase nanocomposite may find extensive application in dye-sensitized solar cells, sensors, and supercapacitors.     

Molecular assembled self-doped polyaniline copolymer ultra-thin films

A self-assembly technique and copolymerization were used to buildup a self-doped polyaniline (SPANI) ultra-thin film on an indium-tin oxide (ITO) substrate. The monomers used were aniline and its derivative MSAN (m-aminobenzenesulfonic acid). Successful MSAN/AN copolymerization and film formation were simultaneously performed in aqueous solution with the addition of oxidant (APS, ammonium persulfate). The film deposition rate of a high AN/MSAN ratio system is generally higher than that of a low AN/MSAN ratio system. Cyclic voltammetry, UV-vis spectroscopy, and α-step instruments indicate a systematic dependence of the film thickness of these ultra-thin films on the assembly time and temperatures. The Auger depth profile reveals the elemental distribution in these films and exhibits different deposition rates between AN and MSAN. XPS N_1s spectra also show the variation of the degree of doping. This SPANI film can be used as an electrochromic electrode in a corresponding device. Carboxyl-terminated-butadiene-acrylonitrile (CTBN) blended with LiClO₄ was used as a solid polymer electrolyte. A total solid electrochromic device was assembled as ITO/SPANI/LiClO₄-CTBN/PEDOT:PSS/ITO, where PEDOT:PSS is poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) as the counter complementary electrode. The device was pale gray at −1.5 V and blue at +1.5 V.     

Nanofibers of self-doped polyaniline

Self-doping polyaniline (SPANI) nanofibers were synthesized by using self-assembly process consisting of a self-doping monomer (o-aminobenzenesulfonic acid, SAN) and aniline (AN). SAN plays the key roles of a self-doping monomer and a surfactant in the process of forming nanofibers. TEM and SEM results revealed that the morphology, average diameter of the resulting nanofibers depended on the mole ratio of AN to SAN and reaction conditions. NMR, FTIR, XPS, UV-vis spectra were used to describe the molecular structures of the nanofibers. X-ray diffraction was used to characterize the crystallinity in these structures. Results revealed that the molecular structures of polymer chains were similar to those of the emeraldine form of polyaniline (PANI). The doping degree ranged from 21 to 27% corresponding to the AN/SAN mole ratio from 4 to 1.     

共价功能化POSS/PDMS防腐复合涂层的研究

首先采用硅烷偶联剂通过水解缩合反应方法合成氨基功能化倍半硅氧烷(POSS-NH₂),利用其表面氨基通过表面接枝聚合方法在倍半硅氧烷表面接枝磺化聚苯胺以实现其共价功能化,将磺化聚苯胺功能化倍半硅氧烷和聚二甲基硅氧烷通过溶液共混,利用滴涂法在Q235钢材表面制备出疏水防腐涂层。通过核磁共振(NMR)和傅里叶转换红外光谱(FT-IR)对氨基功能化倍半硅氧烷和磺化聚苯胺功能化倍半硅氧烷的结构进行表征分析;利用光电子能谱(XPS)分析磺化聚苯胺功能化倍半硅氧烷的化学组成和元素含量比例;利用扫描电子显微镜(SEM)表征磺化聚苯胺功能化倍半硅氧烷的微观形貌,观察到表面形貌较规整、呈颗粒状、纤维较粗的结构;采用静态接触角测试分析了四种涂层的疏水性,制备出的共价功能化POSS/PDMS防腐复合涂层疏水性最佳,接触角达到115°;采用EIS电化学阻抗谱和Tafel极化曲线测试表征了四种涂层的耐腐蚀性能,结果表明:共价功能化POSS/PDMS防腐复合涂层的腐蚀电位更大,腐蚀电流密度较小,由此表明所制备的材料具有优异的防腐性能。并且发现涂层的接触角越大,防腐性能越好。