Synthesis and characterization of polyaniline/activated carbon composites and preparation of conductive films

Polyaniline was synthesized via polyaniline/activated carbon (PANI/AC) composites by in situ polymerization and ex situ solution mixing. PANI and PANI/AC composite films were prepared by drop-by-drop and spin coating methods. The electrical conductivities of HCl doped PANI film and PANI/AC composite films were measured according to the standard four-point-probe technique. The composite films exhibited an increase in electrical conductivity over neat PANI. PANI and PANI/AC composites were investigated by spectroscopic methods including UV–vis, FTIR and photoluminescence. UV–vis and FTIR studies showed that AC particles affect the quinoid units along the polymer backbone and indicate strong interactions between AC particles and quinoidal sites of PANI. The photoluminescence properties of PANI and PANI/AC composites were studied and the photoluminescence intensity of PANI/AC composites was higher than that of neat PANI. The increase of conductivity of PANI/AC composites may be partially due to the doping or impurity effect of AC, where the AC competes with chloride ions. The amount of weight loss and the thermostability of PANI and PANI/AC composites were determined from thermogravimetric analysis. The morphology of particles and films were examined by a scanning electron microscope (SEM). SEM measurements indicated that the AC particles were well dispersed and isolated in composite films.     

Dielectric behavior of polyaniline–CNTs composite in microwave region

Films of polyaniline (PANI) and polyaniline–CNTs composites have been synthesized by solution casting technique. Fourier transform infrared spectroscopic studies of PANI and PANI–CNTs composite films indicated the presence of interaction between CNTs and molecular chains of PANI. Dielectric properties of PANI and composite films have been investigated in the frequency range of 8.0–12.0 GHz. The real part of permittivity (ε′) and loss factor (tan δ) were found to be higher in PANI–CNTs composite films as compared to the PANI film. The increasing behavior of ε′ and tan δ has been attributed to the interaction present between CNTs and PANI molecular chains and increase of conductivity of PANI films after incorporation of CNTs.     

Electrical and morphological characterization of polyaniline/sulfonated poly(arylene ether sulfone) composite films

Electrically conductive polyaniline/sulfonated poly(arylene ether sulfone) (PANI/BPS-35) composites were prepared. The influence of humidity and temperature on electrical conductivity of 20 wt% polyaniline containing composite films was tested. The conductivity increment from 17 mS/cm to 44 mS/cm was observed when the temperature increased from 24 °C to 80 °C at 50% relative humidity (RH). The maximum conductivity was 53 mS/cm at 80 °C and 70% RH. Aluminum (Al) and gold (Au) contacts were deposited onto PANI/BPS composite films and their contact properties have been investigated. While Al contacts behave like Schottky type contact, Au contacts showed nearly ohmic characterization. Scanning electron microscopy technology was used to investigate the morphology of PANI/BPS-35 composite films.     

Electrochemical fabrication of polyaniline/multi-walled carbon nanotube composite films for electrooxidation of methanol

Polyaniline (PANI)/multi-walled carbon nanotubes (MWNTs) composite films were fabricated by electropolymerization of aniline containing well-dissolved MWNTs. The films can be used as catalyst supports for electro-oxidation of methanol. Cyclic voltammogram and Chronoamperogram results show that platinum particles deposited on PANI/MWNT composite films exhibit higher electrocatalytic activity towards methanol oxidation than that deposited on pure PANI films. The porous structure and electrical conductivity of PANI films has been significantly changed by introduction of MWNTs, higher surface areas of PANI/MWNT composites has been achieved therefore. It favors for platinum particles to be highly dispersed on the PANI/MWNT composite films and the better electrocatalytic activity of Pt/PANI/MWNT electrode is induced consequently.     

Effect of different carbon fillers and dopant acids on electrical properties of polyaniline nanocomposites

Electrically conducting nanocomposites of polyaniline (PANI) with carbon-based fillers have evinced considerable interest for various applications such as rechargeable batteries, microelectronics, sensors, electrochromic displays and light-emitting and photovoltaic devices. The nature of both the carbon filler and the dopant acid can significantly influence the conductivity of these nanocomposites. This paper describes the effects of carbon fillers like carbon black (CB), graphite (GR) and muti-walled carbon nanotubes (MWCNT) and of dopant acids like methane sulfonic acid (MSA), camphor sulfonic acid (CSA), hydrochloric acid (HCl) and sulfuric acid (H₂SO₄) on the electrical conductivity of PANI. The morphological, structural and electrical properties of neat PANI and carbon–PANI nanocomposites were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT–IR), UV–Vis spectroscopy and the four-point probe technique, respectively. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) studies were also conducted for different PANI composites. The results show that PANI and carbon–PANI composites with organic acid dopants show good thermal stability and higher electrical conductivity than those with inorganic acid dopants. Also, carbon–PANI composites generally show higher electrical conductivity than neat PANI, with highest conductivities for PANI–CNT composites. Thus, in essence, PANI–CNT composites prepared using organic acid dopants are most suitable for conducting applications.     

Fabrication of conductive network formed by polyaniline-ZnO composite on fabric surfaces

A conductive network consisting of polyaniline (PANI) and PANI/nm-ZnO immobilized on the surfaces of poly(ethylene terephthalate) (PET) fabrics was synthesized by a route involving a wet-chemical technique and in-situ chemical oxidative polymerization procedures. Morphological, structural, thermal and electrical properties of the PET fabrics modified with PANI-ZnO composites were analyzed. X-ray diffraction (XRD) measurements of the composites revealed that the crystal structure of incorporated ZnO undergone a weak distortion during the polymerization reaction and the XRD pattern of PANI was predominate. Attenuated total reflection Fourier transform infrared spectroscopic studies indicated the presence of interaction between ZnO nanorods and molecular chains of PANI in the ZnO/PANI layers. Field emission scanning electron microscope images implied the thin composite layers showed a submicro-sized rod like network and the homogeneous distribution on the substrates. Thermogravimetric studies exhibited that the PET-ZnO/PANI composite had a higher thermal stability than anyone of PET and PET-PANI. The surface resistance of ZnO/PANI conductive films was found to be smaller than the PANI film, which was declined as aniline concentration in adsorption bath increased and reached a relatively low value when Zn(NO₃)₂ concentration was at 0.03 mol/L in the precursor solution.     

导电聚苯胺纳米纤维对聚乙烯/炭黑复合体系电阻行为的影响

采用水溶液氧化聚合和热掺杂相结合的技术制备十二烷基苯磺酸掺杂的聚苯胺(PANI-DBSA)纳米纤维,并将PANI-DBSA纳米纤维与低密度聚乙烯(LDPE)和炭黑(CB)进行熔融共混制得PANI-DBSA/LDPE/CB导电复合材料,研究了PANI-DBSA纤维的引入对导电复合材料电阻行为的影响。结果表明,添加PANI-DBSA纳米纤维,复合材料的逾渗阀值移向较低炭黑含量,复合材料的PTC强度得到一定程度的提高,复合材料的电阻率-温度曲线的热循环稳定性得以改善。     

Influence of polyaniline and phthalocyanine hole-transport layers on the electrical performance of light-emitting diodes using MEH-PPV as emissive material

The influence of layer-by-layer films of polyaniline and Ni-tetrasulfonated phthalocyanine (PANI/Ni-TS-Pc) on the electrical performance of polymeric light-emitting diodes (PLED) made from (poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene]) (MEH-PPV) is investigated by using current versus voltage measurements and impedance spectroscopy. The PLED is composed by a thin layer of MEH-PPV sandwiched between indium tin oxide (ITO) and aluminum electrodes, resulting in the device structure ITO/(PANI/Ni-TS-Pc)_n/MEH-PPV/Al, where n stands for the number of PANI/Ni-TS-Pc bilayers. The deposition of PANI/Ni-TS-Pc leads to a decrease in the driving voltage of the PLEDs, which reaches a minimum when n = 5 bilayers. In addition, impedance spectroscopy data reveal that the PLED impedance decreases as more PANI/Ni-TS-Pc bilayers are deposited. The PLED structure is further described by an equivalent circuit composed by two R-C combinations, one for the bulk and other for the interface components, in series with a resistance originated in the ITO contact. From the impedance curves, the values for each circuit element is determined and it is found that both, bulk and interface resistances are decreased upon PANI/Ni-TS-Pc deposition. The results indicate that PANI/Ni-TS-Pc films reduce the contact resistance at ITO/MEH-PPV interface, and for that reason improve the hole-injection within the PLED structure.     

Enhanced thermoelectric properties in polyaniline composites with polyaniline-coated carbon nanotubes

Polyaniline (PANI)-coated multi-walled carbon nanotubes (PANI-CNTs) were firstly synthesized by in situ polymerization and then incorporated into the PANI matrix by hot pressing to fabricate bulk PANI-CNT/PANI composites. The composites showed homogeneously dispersed CNTs into the PANI matrix with a strong interface interaction. Thermoelectric measurements at room temperature showed a significant enhancement in both the electrical conductivity and Seebeck coefficient with the addition of PANI-CNTs. At the same time, relatively low thermal conductivity was also obtained. The maximum electrical conductivity and Seebeck coefficient of the composites were up to 2.8 × 10³ S/m and 21.6 μ/K, respectively, and the maximum figure of merit reached 1.0 × 10^?3 more than three orders of magnitude higher than that of neat PANI. This study proposed a novel and effective way to fabricate bulk PANI/CNT composites with enhanced thermoelectric properties.     

Percolation effect and thermoplasticity of conducting [poly(acrylic acid)/C16TAB-modified graphene oxide]n multilayer films

The feasibility and effectiveness of the electrostatic self-assembly technique are demonstrated for the fabrication of thermoplastically conducting multilayer films. The layer-by-layer self-assembly process is based on the alternating adsorption of low molecular weight (M _n) poly(acrylic acid) (PAA) and cetyltrimethyl-ammonium bromide-modified graphene oxide (GO) with three carbon layers. A unique conductivity percolation effect is observed at a percolation threshold (percolation bilayer number) because the carbon–carbon interlayer can be expanded by the diffusion of PAA molecular chains. The resultant multilayer films show typical positive/negative temperature coefficient effects because of the thermoplasticity of the PAA with low M _n. After being reduced from GO to graphene (G), the electrical conductivity of the resulting (PAA/G)_n multilayer film is dramatically enhanced, and the percolation threshold occurs at a high bilayer number. The reasonable conductivities and the percolation effect make these films inherently interesting and potentially useful as components of advanced electronic devices.     

All-organic PANI–DBSA/PVDF dielectric composites with unique electrical properties

Novel all-organic polymer high-dielectric permittivity composites of polyaniline (PANI)/poly (vinylidene fluoride) (PVDF) were prepared by solution method and their dielectric and electric properties were studied over the wide ranges of temperatures and frequencies. To improve the interface bonding between two polymers, dodecylbenzenesulfonic acid (DBSA), a bulky molecule containing a polar head and a long non-polar chain was used both as a surfactant and as dopant in polyaniline (PANI) synthesis. Synthesized conducting PANI–DBSA particles were dispersed in poly(vinylidene fluoride) (PVDF) matrix to form an all-organic composite with different PANI–DBSA concentrations. Near the percolation threshold, the dielectric permittivity of the composites at 100 Hz frequency and room temperature was as high as 170, while the dielectric loss tangent value was as low as 0.9. Like typical percolation system, composites experienced high dielectric permittivity at low filler concentrations. However, their dielectric loss tangent was low enough to match with non-percolative ceramic filler-based polymer composites. Maximum electrical conductivity at 24 wt% of PANI–DBSA was mere 10^?6 S/cm, a remarkably low value for percolative-type composites. Increase in the dielectric permittivity of the composites with increase in temperature from 25 to 115 °C for different PANI–DBSA concentrations was always in the same range of 50–60 %. However, the degree of increase in the electrical conductivity with the temperature was more prominent at low filler concentrations compared with high filler concentrations. Distinct electrical and their unique thermal dependence were attributed to an improved interface between the filler and the polymer matrix.     

Formation and surface modification of self-assembled films with acrylated hyperbranched poly(ester-amine) as the outmost layer

An acrylated hyperbranched poly(ester-amine) (HPEA) synthesized from piperazine and trimethylolpropanetriacrylate at a molar ratio of 1:1.42 was used as the polycation to form self-assembled films by layer-by-layer dipping with poly(sodium-p-styrenesulfonate) as the polyanion. The surface morphology and hydrophilicity of the films with HPEA as the outmost layer were controlled by adjusting the solution pH of HPEA. Due to the existence of many acrylate groups, the films with HPEA as the outmost layer were further reacted with a series of reagents, including piperazine, piperidine, laurylamine and p-phenylenediamine. The surface reactions of the films depended on both the nature of the reagents and the morphology of the initial surface. In the presence of the strong basic amines, piperazine and piperidine, the films dissolved extensively into the solution. In the case of laurylamine, a modified film with an opaque appearance was obtained due to the crystallization of long alkyl chains. With the weak basic amine p-phenylenediamine as the reactant, the film was effectively modified without any change in the surface morphology.     

Preparation and characterization of novel polypyrrole-nanotube/polyaniline free-standing composite films via facile solvent-evaporation method

Polyaniline (PANI) is an important conducting polymer and has drawn much attention for its inexpensiveness and chemical stability in the conducting state but its conductivity is rather low. Another well-known conducting polymer is polypyrrole (PPy) with a much higher electrical conductivity but it is hard to prepare films using PPy alone due to its poor film-forming ability. In this work, novel polypyrrole-nanotube (PPy-NT)/polyaniline (PANI) composite films are prepared via a facile solvent-evaporation method. The influence of the PPy-NT content is examined on the film structure, morphology, electrical and mechanical properties. It is shown that PPy nanotubes (PPy-NTs) are uniformly distributed in the PANI matrix. The electrical conductivity is greatly enhanced by 10.2 times by the addition of 10 wt.% PPy nanotubes. Moreover, the mechanical ductility is significantly increased by the addition of PPy nanotubes.     

Synthesis and electrical properties of polymer composites with polyaniline nanoparticles

Nano-sized polyaniline (PANI) particles dispersed in aqueous solution were prepared using both poly(vinyl alcohol) (PVA) and poly(styrene sulfonic acid) (PSSA) as polymeric stabilizers. Size of the spherical PANI particle synthesized using PVA with a HCl dopant (PANI-HCl/PVA) was about 150 nm in diameter, and that with PSSA (PANI-PSSA) was about 50 nm, with a uniform size distribution. Doping level of the PANI-PSSA measured by UV–visible spectrometer was higher than that of PANI-HCl/PVA. The PVA based composite films using both PANI-HCl (PANI-HCl/PVA) and PANI-PSSA (PANI-PSSA/PVA) were prepared by a casting method for different PANI content and their electrical conductivities were measured. A percolation threshold of PANI concentration for conductivity of composite was found only around 10 wt.% of PANI for the PANI-PSSA/PVA, and furthermore, the PANI-PSSA/PVA became more conductive above the threshold point than PANI-HCl/PVA.     

Studies on conductivity and dielectric properties of polyaniline-zinc sulphide composites

In the present paper, we report electrical conductivity and dielectric studies on the composites of conducting polyaniline (PANI) with crystalline semiconducting ZnS powder, wherein PANI has been taken as inclusion and ZnS crystallites as the host matrix. From the studies, it has been observed that the value of room temperature d.c. conductivity of the composites with volume fraction of PANI > 0.65 shows an unusual behaviour wherein, conductivity values of the composites exceed that of PANI itself with maximum value as high as 6 times that of PANI at the volume fraction of 0.85. A similar trend has also been observed for the real and imaginary parts of complex dielectric constant values of the composites. This unusual behaviour in the d.c. conductivity and dielectric properties has been attributed to the enhancement in the degree of crystallinity of PANI as a consequence of its interfacial interaction with ZnS matrix. The results of optical microscopy show coating of PANI all around the ZnS particles. The temperature dependent conductivity studies suggest the quasi one-dimensional VRH conduction in PANI as well as its composites with ZnS. FTIR and XRD studies have also been reported.     

Interaction of oxygen with nanocomposites made of n-type conducting polymers and carbon nanotubes: role of charge transfer complex formation between nanotubes and poly(3-octylthiophene)

Photo-induced conductivity changes in n-doped poly(3-octylthiophene) (P3OT)/single-walled carbon nanotube (SWNT) composites have been examined. When exposed simultaneously to ultraviolet (UV) light and oxygen, carbon nanotubes exhibit photo-induced oxidation. An analysis of n-doped P3OT/SWNT composite exposed to oxygen/UV shows that conductivity increases and that charge carrier mobility is governed by the formation of a charge transfer complex. Possible sites of oxygen photoadsorption and its implications on the observed electrical properties of nanocomposite are considered.     

Electrical and mechanical properties of antistatic PVC films containing multi-layer graphene

In order to explore practical application of graphene as novel conductive fillers in the filed of composite materials, we prepared anti-static multi-layer graphene (MLG) filled poly(vinyl chloride) (PVC) composite films by using conventional melt-mixing method, and investigated electrical conductivity, tensile behavior, and thermal properties of the MLG/PVC composite films. We found that the presence of MLG can greatly increase electrical conductivity of the MLG/PVC composites, and the surface electrical conductivity of the MLG/PVC composites is less than 3 × 10⁸ Ohm/square when the MLG loading is about 3.5 wt%, meeting anti-static requirement for commercial anti-static PVC films. On the other hand, the MLG/PVC composites exhibited higher tensile modulus and higher glass transition temperature than neat PVC, which is closely associated with crumpled morphology of the MLG and good compatibility between components of the MLG/PVC composites. By virtue of its satisfied anti-static performance and high mechanical properties, the MLG/PVC composites exhibit great potential to be used as high-performance antistatic materials in many fields.     

Processible polyacid doped polyaniline composites: Application for charge storage devices

Processible polyaniline (PANI) composites with a polyacid (polyacrylic acid, PAA) are synthesized and studied for their structural, electrical and electrochemical properties. The material is used for the first time for development of electrochemical capacitor. The processible conducting composites have been prepared by mixing the polyaniline and polyacrylic acid in various weight percentage from 20 wt.% to 90 wt. % (of polyaniline) under vigorous stirring and sonication conditions. Self-standing films of these electroactive and homogeneous composites were obtained by solution casting method. A significant improvement in processibility, crystallinity and stability was observed in the composites having PANI up to 90 wt.% of total content. However, the electrical conductivity decreased remarkably as the percentage of PANI decreased in the composites. The composite having 60 wt.% PANI in PAA showed very interesting structural property as it is found to be highly crystalline with orthorhombic crystal system and cell parameters as a = 5.93 Å, b = 7.57 Å and c = 10.11 Å. The composites are used for the development of electrochemical capacitors. The 60 wt.% PANI-PAA composite showed highest capacitance amongst all the composites and used as an active material for development of an electrochemical capacitor using a parallel plate assembly.     

Preparation and fuel cell performance of catalyst layers using sulfonated polyimide ionomers

Sulfonated polyimide (SPI-8) ionomers were used as binders in the catalyst layers, and their fuel cell performance was evaluated. SPI-8 ionomers functioned well in the anode with only minor overpotential even at low humidity (50% relative humidity (RH)). In contrast, the cathode performance was significantly dependent on the content and molecular weight of the ionomers and humidity of the supplied gases. Higher molecular weight of the ionomer caused larger potential drop at high current density at 80 and 100% RH since oxygen supply and/or water discharge became insufficient due to higher water uptake (swelling) of the ionomer. Similar results were obtained at higher ionomer content, because of the increase of thickness in the catalyst layer. The mass transport was improved with decreasing humidity, however, proton conductivity became lower. While the maximum values of j(@0.70?V) for all membrane electrode assemblies (MEAs) were ca. 0.35 A/cm(2), each electrode could have the different appropriate operating conditions. The results suggest that the parameters such as oxygen supply, proton conductivity, and water uptake and discharge need to be carefully optimized in the catalyst layers for achieving reasonable cathode performance with hydrocarbon ionomers.     

Influence of NiCr/Au electrodes and multilayer thickness on the electrical properties of PANI/PVS ultrathin film grown by Lbl deposition

In the present work, we concentrate on the study of effects of metallic electrodes, multilayer thickness and temperature in ac and dc electrical conductivity of polyaniline/poly(vinyl sulfonic acid) (PANI/PVS) ultrathin films. The polymer system was obtained from layer-by-layer (Lbl) self-assembly technique on a glass substrate with an electrode array of adhesion layer of NiCr (20 nm) covered with Au (180 nm). We observed a significant and abrupt increase in the value of dc conductivity and a change of ac conductivity behavior of NiCr/Au-PANI/PVS-NiCr/Au structure when the thickness of PANI/PVS system reaches the Au layer. These effects were ascribed to the ideal contact of Au-PANI/PVS and the relative high interfacial contact resistance between PANI/PVS and NiCr, thus reducing the parallel resistance of NiCr/Au-PANI/PVS interfacial layer in an ideal parallel plate capacitor structure. Atomic Force Microscopy images confirm this assumption. Furthermore, the ac conductivity of Au-PANI/PVS-Au structure was typical of solid disordered materials. A model based on carrier hopping in a medium with randomly varying energy barriers was presented for the ac conductivity of the polymer system, which also encompasses the high dielectric constant of PANI/PVS blended films, the neutral contact Au-PANI/PVS, and the electrical resistance of NiCr-PANI/PVS interfacial layer. The model allowed separating the interface and the bulk effects in the electrical response of NiCr/Au-PANI/PVS-NiCr/Au structure and in addition the highest activation energy (35 MeV) correlated with an optimization of hopping distance (30 nm) for carriers jumps in PANI/PVS system.