In situ surface modification of natural fiber by conducting polyaniline

Newly modified biofibers made up of kenaf fibers (KF) and conducting polyaniline (PANI) were successfully prepared via in situ polymerization. Several characterization methods were done to elucidate the interaction between the KF surfaces and the in situ polymerized PANI. The PANI coated KF (KF/PANI) achieved new electronic properties, without sacrificing its mechanical properties and natural fiber characteristic. Initial mercerization on the KF yielded better PANI coated fibers compared to the untreated KF. Fiber bundle tensile test on the untreated KF/PANI revealed a drop in the unit break of about 48% compared to the untreated neat KF. Meanwhile, the mercerized KF/PANI showed reduction of about 17% compared to the uncoated mercerized KF. The mercerized KF/PANI exhibits polaronic transitions, existence of favorable IR peaks and Raman scattering, enhanced DC conductivity, and better morphological characteristic as a result of the in situ PANI coating. Such electronically modified natural fibers could be suitable as green conducting fillers in composites to replace other synthetic fibers.     

Preparation and characterization of conductive nanostructured particles based on polyaniline and cellulose nanofibers

Conducting polyaniline (PANI) and cellulose coated PANI (PANI-NC) nanostructures with sizes of about 80–100 nm, doped with hydrochloric acid were synthesized by a sonochemical method. Both type of particles resulted electrically conductive (direct current conductivity of 0.059 and 0.075 S/cm for PANI and PANI-NC structures, respectively) and could be dispersed easily in water, leading to green colored suspensions that remain stable for more than 4 h. The morphology, crystallinity, electrical conductivity (σ) and thermal stability of the obtained PANI based structures were investigated and compared. Furthermore, UV–Vis spectroscopy and rheology of water suspensions were used to explain the measured properties. Although the concentration of cellulose fibers used to synthesize the PANI-NC structures was very low, important differences respect to the neat PANI fibers regarding the microstructure, electrical conductivity and suspension behavior were found.     

Dielectric and impedance studies of DBSA doped polyaniline/PVC composites

Polyaniline (PANI) was doped with dodecylbenzene sulfonic acid (DBSA) and then mixed with PVC by solution blending method to prepare DBSA doped PANI (PAND)/PVC composites. FTIR spectroscopy indicates the strong dipole–dipole interaction between the individual components of the composites. The ac electrical properties of the synthesized composites were investigated by complex impedance spectroscopy in the frequency range of 0.5–10⁶ Hz at room temperature. Both dielectric loss factor and permittivity increase with the decrease of frequency exhibiting strong interfacial polarization at low frequency. Addition of PAND in PVC reduces the charge trapping centers by increasing the number of conducting channels participating in the relaxation process; hence an increase in conductivity is observed.     

Structural and electrical studies on PVDF:PANI composite thin films and their application as buffer layer on hybrid solar cells

Hybrid (organic–inorganic) solar cells were fabricated and tested using buffer layer of polyaniline (PANI)–poly(vinylidene difluoride) (PVDF) composites. The effect of PANI:PVDF composite on the performance of the solar cells was explored and the cells were characterized by current voltage (I?V) measurements under a solar simulator generating AM1.5 light (1000?W/m²) irradiance. It was found that solar cells containing ITO/PANI:PVDF photo-anode are likely to improve photocurrent and power conversion efficiency in a way superior to that containing only ITO as photo-anode. Furthermore, PANI:PVDF composite enhanced the hole extraction at photo-anode/photo-active layer interface via the high electrical conductivity of PANI and the ferroelectricity of PVDF.     

Electrical conductivity and dielectric properties of sulfamic acid doped polyaniline

The temperature and frequency dependence of dielectric constant (ε′) and dielectric loss (ε″) is studied for different samples of polyaniline (PANI), doped with different concentration of sulfamic acid in the frequency range (10–100 kHz) and temperature range (300–400 K). The dc conductivity has also been measured to see the effect of sulfamic acid and the conduction mechanism has been explained by the propagation of polaron through a conjugated polymer chain due to shifting of double bonds (alternation), which gives rise to electrical conduction.     

Surface modification of polyacrylonitrile film by anchoring conductive polyaniline and determination of uricase adsorption capacity and activity

Polyacrylonitrile (PAN) films were modified with chemical polymerization of conductive polyaniline (PANI) in the presence of potassium dichromate as an oxidizing agent. The effect of aniline concentration on the grafting efficiency and on the electrical surface resistance of PAN and (PAN/PANI)-1-3 composite film was investigated. The surface resistances of the conductive composite films were found to be between 6.32 and 0.97 kΩ/cm. As the amount of grafted PANI increased on the PAN films, the electrical resistance of composite film decreased. The PAN/PANI composite films were also characterized using SEM and FTIR. The changes in the surface properties of the films were characterized by contact angle measurements. As expected, the PAN, PAN/PANI and PAN/PANI-uricase immobilized films, exhibited different contact angle values and surface free energy due to different interactive functional groups of the films.The conductive films were well characterized and used for immobilization of uricase. The amount of adsorbed enzyme increases with the increase of surface concentration of grafted fibrous polyaniline polymer. The maximum amount of immobilized enzyme onto composite film containing 2.4% PANI was about 216 μg/cm² (i.e., PAN/PANI-3). The immobilized uricase was reused 24 times in batch wise assay in a day. Finally, the immobilized uricase enzyme system was successfully fabricated and applied to determine the uric acid level in human serum samples.     

Simultaneously depositing polyaniline onto bacterial cellulose nanofibers and graphene nanosheets toward electrically conductive nanocomposites

In this study, we report the construction of a ternary flexible nanocomposite of bacterial cellulose/graphene/polyaniline (BC/GE/PANI) via a facile two-step strategy. Bacterial cellulose/graphene (BC/GE) is first prepared by a novel in situ membrane-liquid-interface method, in which the three-dimensional continuous BC nanofibers can be maintained and the introduced GE can improve the mechanical properties mainly due to the uniform dispersion of GE in the BC matrix. To construct the effectively interconnected conductive paths between separated GE nanosheets, polyaniline (PANI) is simultaneously deposited on the surfaces of both BC nanofibers and GE nanosheets to obtain BC/GE/PANI with excellent electrical conductivity. It is found that the as-prepared BC/GE/PANI has an electrical conductivity of 1.7 ± 0.1 S cm⁻¹, which is higher than most of PANI-based composites. It is believed that the BC/GE/PANI nanocomposite possesses great potential for applications in electromagnetic shielding and flexible electrodes.     

Chitosan-ZnO/polyaniline ternary nanocomposite for high-performance supercapacitor

We report on the synthesis of chitosan-zinc oxide (ZnO)/polyaniline (CS-ZnO/PANI) ternary nanocomposites via in situ polymerization of aniline in the presence of CS-ZnO nanocomposite prepared by simple precipitation method. The structure, morphology, and physicochemical properties of prepared ternary composites are characterized by Fourier transform infrared, UV–visible, X-ray diffraction, SEM, EDXS, TEM, thermogravimetric/differential thermal analysis, and N₂ adsorption/desorption measurements. Their electrochemical properties are also investigated using cyclic voltammetry, galvanostatic charge–discharge tests, and electrochemical impedance spectroscopy. Electrochemical measurements show that the mesoporous CS_0.12-ZnO_2.5/PANI electrode yields larger specific capacitance (587.15 F g^?1) than the corresponding PANI-ZnO electrode without added chitosan and the capacitance retention is 80 % after 1,000 charge/discharge cycles at 175 mA cm^?2 current density in the voltage range of 0 to 0.8 V vs. SCE, due to the synergistic effect among three components which result in enhanced specific capacitance and cycling stability. The resulting composites are promising electrode materials for high-performance, environmentally friendly, and low-cost electrical energy storage devices.     

Positron beam studies on polyaniline and Ag-coated polyaniline

The effect of doping of the polyaniline emeraldine base (PEB), with Ni as well as Ni over layer coating has been investigated using variable low energy positron beam. Depth-resolved Doppler S-parameter measurements have been performed on undoped, Ni-doped polyaniline (PANI), and Ag (40 nm) film deposited PANI samples. Significant variation in S-parameter is observed for undoped and Ni-doped PANI. The size of the free volume hole has shifted to lower values upon doping with Ni as compared to that of undoped PANI, which is consistent with the conductivity measurements. For Ag-coated PANI systems, the S vs. E_p curves show distinct changes at the surface and interior regions. These results are discussed in the light of changes in free volume hole size distribution.     

EPR investigations of silicon carbide nanoparticles functionalized by acid doped polyaniline

Nanocomposites (SiC-PANI) based on silicon carbide nanoparticles (SiC) encapsulated in conducting polyaniline (PANI) are synthesized by direct polymerization of PANI on the nanoparticle surfaces. The conductivity of PANI and the nanocomposites was modulated by several doping levels of camphor sulfonic acid (CSA). Electron paramagnetic resonance (EPR) investigations were carried out on representative SiC-PANI samples over the temperature range [100–300 K]. The features of the EPR spectra were analyzed taking into account the paramagnetic species such as polarons with spin S=1/2 involved in two main environments realized in the composites as well as their thermal activation. A critical temperature range 200–225 K was revealed through crossover changes in the thermal behavior of the EPR spectral parameters. Insights on the electronic transport properties and their thermal evolutions were inferred from polarons species probed by EPR and the electrical conductivity in doped nanocomposites.     

Charge‐transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy

Highly dispersed nanocomposites of polyaniline(PANI) and oxidized single wall carbon nanotubes(SWNTs) have been prepared using dodecylbenzenesulfonic acid as dispersant. The materials were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was also investigated using in situ Raman electrochemical measurements. The results obtained at E_laser = 1.17 eV suggest that a charge‐transfer process occur between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized. The spectroelectrochemical data show that the presence of SWNTs prevents the oxidation of PANI rings. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of organic soluble polyaniline prepared by one-step emulsion polymerization

Emeraldine salt of polyaniline-dodecylbenzenesulfonic acid (PANI-DBSA) in organic solvents such as toluene and xylene was obtained by a direct one-step emulsion polymerization technique. When the molar ratio of DBSA to aniline monomer was 1.5:1, solubility and electrical property showed a maximum value. The solid contents of PANI-DBSA was 8 wt.% in toluene. The casting film of PANI-DBSA was obtained on glass or plastic substrate under ambient conditions. PANI solution can also be easily blended with polyurethane and polystyrene polymers in toluene. Better electrical performance (up to 5 S/cm), good light transmittance (up to 70% at 500 nm thickness), were obtained and more homogeneous morphology was observed for the casting film of PANI-DBSA prepared by the present method as compared with that prepared by the aqueous emulsion polymerization. The partially dispersed PANI-DBSA particles of 50–400 nm sizes in organic solvents such as toluene and xylene were observed and the crystalline nature of these powder samples was confirmed from the XRD patterns.     

Preparation and characterization of polyaniline+TiO2 composite films

In this work, we have prepared electrochemically and studied a composite materials based on an organic conducting polymer, polyaniline (PANI), in which inorganic semiconductor titanium dioxide (TiO₂) particles were incorporated with different concentrations. The polyaniline/titanium dioxide composite material which had been deposited by cyclic voltammetry on substrates of indium tin oxide was then characterized. The cyclic voltammogram showed one redox couple characteristic of the oxidation and reduction states of the produced composite material. The impedance spectroscopy study showed that the resistance of the film increases with the TiO₂ cocntent incorporated in the polymer. The incorporation of TiO₂ in PANI covering the surfaces was confirmed by the scanning electron microscopy and the energy dispersive X-ray analysis. The morphological analysis of the film surfaces showed that the TiO₂ nanoparticle increased the roughness. These observations allow to consider a new approach to improve the physicochemical properties of the interface between the organic and inorganic material. The I–V characteristics of PANI+TiO₂ heterostructure diode showed the nonlinear nature of the I–V curve of PANI+TiO₂ heterostructure device.     

Solid-state magnetic resonance studies of polyaniline as a radical scavenger

The first detailed study of polyaniline (PANI) and reduced PANI (R-PANI) before and after reaction with the stable organic free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH) by using solidstate¹³C CP MAS (cross-polarization magic-angle spinning), NQS (nonquaternary suppressed) and CPPI (cross-polarization phase inversion) nuclear magnetic resonance techniques is reported. These techniques reveal relatively subtle structural changes that occur upon reaction with DPPH free radicals and confirm the radical scavenging ability of PANI. The integrated intensity of the PANI CP MAS spectrum after reaction with DPPH is about 8% larger than that of PANI and this cannot be explained by an oxidation process alone. The increase is attributed to a decrease in the polaron concentration in the polymer, which is consistent with electron paramagnetic resonance (EPR) data that show a decrease of the EPR signal intensity after reaction of chemically synthesized PANI with DPPH.     

Preparation of highly conductive CNTs/polyaniline composites through plasma pretreating and in-situ polymerization

In this study, carbon nanotubes (CNTs) were pretreated by plasma, and further in-situ polymerized with aniline to achieve uniform CNTs/polyaniline (PANI) composites with high conductivity. The highest conductivity (2.946 S/cm) of CNTs/PANI composites under optimum plasma treating parameters is much higher than those without CNTs pretreatment or premodified by acid oxidation method. The scanning electronic microscope (SEM) pictures indicate that smooth surfaces of pristine CNTs (diameter: 20-40 nm) changes into rough structures and the size increases to around 90 nm, which is further proved by the X-ray diffraction (XRD), the Fourier transform infrared spectroscopy (FTIR), and the Raman measurements. Thermogravimetric analysis (TGA) results reveal that the thermal stability of CNTs/PANI composite is better than that of pure PANI.     

Unique dielectric properties in polyaniline/poly(vinylidene fluoride) composites induced by temperature variation

To explore an effect of temperature on the dielectric properties in polyaniline/poly(vinylidene fluoride) (PANI/PVDF) composites, the dielectric properties of these composites with different volumetric fractions of PANI (?_PANI) were studied in a wide temperature range. An increase in the effective conductivity (σ_eff) and dielectric permittivity (?_eff) was observed with increasing temperature in all PANI/PVDF composites. Particularly, for the composite with ?_PANI = 0.01, less than the percolation threshold (?_C = 0.045), the increase in σ_eff and ?_eff was most significant. A tunneling effect could be responsible for the unique dielectric properties. The results provided us useful information related to the microstructure of composites, which was not reported previously. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Application of polyaniline as enzyme based biosensor

The PANI films have been synthesized electrochemically and are used as matrix for immobilization of glucose oxidase (GOD) and lactate dehydrogenase (LDH) enzymes. The temporal aspects of anion self-exchange in PANI films have been investigated. The exchange of bulkier tosylate–ferricyanide ion with Cl⁻ ion has been monitored by photometry and electrochemical techniques. The relative changes in porosity brought about by self-exchange have been experimentally determined to be 323 and 2125/k in tosylate-exchanged and ferricyanide-exchanged polyaniline films, respectively. It is seen that the polyaniline films exhibit enhanced loading of glucose oxidase after a self-ion exchange, and, hence they can be used for the fabrication of a third generation glucose biosensor.Lactate is determined by the photometric detection of NADH formed in the reaction catalysed by LDH. Studies have been carried out with PANI as a matrix for the immobilization of LDH and its feasibility as a biosensor. The results of the photometric and amperometric measurements conducted on such LDH/PANI electrodes show a response to pyruvate concentration upto 0.45 mM, a response time of 90 s and a shelf life of about two weeks.     

Comparative impact of doping nano-conducting polymer with carbon and carbon oxide composites in alkyd binder as anti-corrosive coatings

This study concentrated on producing anticorrosive coating depending on alkyd resin blended with polyaniline-carbon allotropes composites as filler. Polyaniline (PANI) and its composites were produced by doping of PANI with the carbon allotropes (graphene and multi-walled carbon nanotubes) and carbon-oxide allotropes (graphene oxide and multi-walled carbon nanotubes oxide) in different ratios through in situ chemical polymerization. The morphology of PANI and its composites were examined by transmission electron microscope (TEM), which proved that PANI composites appeared as a shell layer in core/shell structure with various overlay thickness depending on the adsorption type for polyaniline. The performance of the prepared coatings in cabinet salt agrees with electrical conductivity values where the best PANI/composite in conductivity value is the most efficient as an anti-corrosive coating.     

Preparation and Characterization of an Organic/Inorganic Composite Based on Ferrospinel with Poly(Methyl Methacrylate) and Polyaniline

A novel organic/inorganic composite based on LiNi–ferrospinel with poly(methyl methacrylate) (PMMA) and polyaniline (PANI), PANI/PMMA/LiNi_0.5Fe₂O₄ composite, was synthesized via a facile in-situ polymerization process. The structures of the resulting samples were investigated by X-ray diffraction, Fourier transform infrared spectroscopy, and atomic force microscopy. The optical and thermal properties of the PANI/PMMA/LiNi_0.5Fe₂O₄ composite were studied by fluorescent spectroscopy and thermogravimetry analysis. It was indicated that the existence of LiNi_0.5Fe₂O₄ (LFNO) in the PANI/PMMA/LFNO composite resulted in changes in the fluorescence spectra. The as-obtained composite may have potential for electrical and electromagnetic applications in antistatic materials, electromagnetic shields, radar absorbers, and so forth.     

Ac and Dc conductivities of polyaniline/poly vinyl formal blend films

The synthesis and characterization of polyaniline (PANI)/poly vinyl formal (PVF) blend films were carried out in this work. Polyaniline base was doped using dodecylbenzene sulfonic acid (DBSA). These blend films were characterized by UV–Visible, FTIR spectra and scanning electron microscopy (SEM) to investigate their optical, structural and morphological properties. It was found that the percolation threshold of these blends is 4.4 wt% of PANI. The dc and ac conductivities of these blend films have been measured at a temperature range from 300 to 100 K in the frequency range of 10 kHz to 1 MHz. The electrical conductivity of the blend films enhanced with the increase of polyaniline amount up to a value of 2.5 × 10⁻⁴ S cm⁻¹ at 65 wt% of polyaniline. The dc conductivity of the PANI/PVF blend films follows the three-dimension variable range hopping. Temperature variation of frequency exponents in this blend suggests that ac conduction is attributed to be correlated barrier hopping.