Volume 67, Issue 8 - Recent trends and progress in research into structure and properties of polyaniline and polypyrrole

In recent years, much research has focused on the development of low-cost, printed electrochemical sensor platforms for environmental monitoring and clinical diagnostics. Much effort in this area has been based on utilising the redox properties of conducting polymers, particularly polyaniline (PANI). In tackling the inherent lack of processability exhibited by these materials, several groups have examined various mass-amenable fabrication approaches to obtain suitable thin films of PANI for sensing applications. Specifically, the approaches investigated over the years include the in situ chemical synthesis of PANI, the use of sulphonated derivatives of PANI and the synthesis of aqueousbased nano-dispersions of PANI. Nano-dispersions have shown a great deal of promise for sensing applications, given that they are inkjet-printable, facilitating the patterning of conducting polymer directly to the substrate. We have shown that inkjet-printed films of PANI can be finely controlled in terms of their two-dimensional pattern, thickness, and conductivity, highlighting the level of precision achievable by inkjet printing. Utilising these nanomaterials as inkjet-printable inks opens novel, facile, and economical possibilities for conducting polymer-printed electronic applications in areas of sensing, but also many other application areas such as energy storage, displays, organic light-emitting diodes. Given that inkjet-printing is a scalable manufacturing technique, it renders possible the large-scale production of devices such as sensors for a range of applications. Several successes have emerged from our work and from the work of others in the area of applying PANI in low-cost sensor applications, which is the focus of this review.

Polyaniline (PANI) and polypyrrole (PPY) undergo carbonisation in an inert/reduction atmosphere and vacuum, yielding different nitrogen-containing carbon materials. This contribution reviews various procedures for the carbonisation of PANI and PPY precursors, and the characteristics of obtained carbonised PANI (C-PANI) and carbonised PPY (C-PPY). Special attention is paid to the role of synthetic procedures in tailoring the formation of C-PANI and C-PPY nanostructures and nanocomposites. The review considers the importance of scanning and transmission electron microscopies, XPS, FTIR, Raman, NMR, and EPR spectroscopies, electrical conductivity and adsorption/desorption measurements, XRD, and elemental analyses in the characterisation of C-PANIs and C-PPYs. The application of C-PANI and C-PPY in various fields of modern technology is also reviewed.

Preparations of hybrid composites composed of two conducting components, a conducting polymer and silver, are reviewed. They are produced mainly by the oxidation of aniline or pyrrole with silver ions. In another approach, polyaniline or polypyrrole are used for the reduction of silver ions to metallic silver. Other synthetic approaches are also reviewed. Products of oxidation of aniline derivatives, including phenylenediamines, are considered. Morphology of both the conducting polymers and the silver in composites displays a rich variety. Conductivity of the composites seldom exceeds 1000 S cm−1 and seems to be controlled by percolation. Interfacial effects are also discussed. Potential applications of hybrid composites are outlined; they are likely to extend especially to conducting inks, printed electronics, noble-metal recovery, antimicrobial materials, catalysts, and sensors.

One of the remarkable applications of conducting polymers is as an electrorheological (ER) fluid which is a smart suspension of polarisable particles dispersed in an insulating liquid with the capacity to effect a phase transition from a liquid-like to a solid-like state. Polyaniline (PANI) and its hybrids with inorganics or other polymers are active candidates for ER materials due to their various advantages, e.g., easy synthesis, controllable conductivity, and less friction than pure inorganics. In this short review, we review recent progress in the synthesis of semi-conducting PANI and its hybrids with diverse morphologies and their ER performance measured by a rotational rheometer using the applied electric field strength. The dielectric properties of these ER fluids, as an important analytical method for their ER performance, are also discussed.

Rechargeable lithium-ion batteries (LIBs) have been the most commonly used batteries in the portable electronics market for many years. Polypyrrole (PPy) was now investigated as a conducting addition agent to enhance the cathode and anode materials performance in LIBs. Actual development in the synthesis and modification of the most promising cathode materials, LiFePO4, is described in this mini-review. The main aim of this mini-review is to highlight the effect of PPy based conducting polymer films on the electrochemical efficiency of LiFePO4 based cathode materials for LIBs summarizing our own research. Influence of the polyethylene glycol (PEG) additive in the PPy coating layer was evaluated. The improved electrochemical performance can be attributed to the enhanced electronic conductivity, higher solubility of ions originating from the electrolyte, higher movability of dissolved Li+ ions, and improved structural flexibility resulting from the incorporation of the PPy or PPy/PEG conducting polymer layer. The stabilizing effect of PEG in PPy was reflected in lowered cross-linking and reduced structural defects and, in consequence, in higher specific capacity of PPy/PEG-LiFePO4 cathodes compared to that of PPy-LiFePO4 cathodes and bare LiFePO4 cathodes.

This article provides a brief overview of recent work by the authors’ group as well as related researches reported by others on controlling the morphology and exploring the formation mechanism of typical micro-/nanostructures of polyaniline (PANI) and aniline oligomers through template-free aniline chemical oxidation process. The contents are organised as follows: (i) tuning the morphology of aniline polymerisation products by employing ultrasonic irradiation, mass transfer, and pH profiles; (ii) exploring the formation mechanism of micro-/nanostructures during aniline chemical oxidation through examining the precipitation behaviours of aniline oligomers and polymers in a post-synthetic system; (iii) tailoring PANI micro-/nanostuctures into pre-designed morphology by introducing certain heterogeneous nucleation centres; (iv) application potential of PANI nanofibres in the areas of transparent conductive film, electromagnetic interference-shielding coating and graphene-based electrode materials. This short review concludes with our perspectives on the challenges faced in gaining the exact formation mechanism of PANI micro-/nanostructures and the future research possibility for morphologically precisely controlled PANI micro-/nanostructures.

Aniline chemical oxidative polymerisation (COP), which produces various polyaniline (PANI) and oligoaniline supra-molecular structures, can be regarded as an in situ self-assembly process. This review provides a brief introduction to recent work on the structural characters and self-assembly behaviours of oligomeric aniline chemical oxidation products; it is focused on the relationships between the oligomeric species and morphology of the final products such as PANI nanoparticles, nanofibres/rods, nanotubes or oligoaniline nanosheets, micro/nanospheres in aniline COP systems. Several mechanisms proposed as explanations for the formation of typical supra-molecular structures are discussed in order to illustrate the roles of aniline oligomers. This article concludes with our perspectives on future work remaining to be done to uncover the formation mechanism of supra-molecular structures constructed by aniline chemical oxidation products and their controllable synthesis.

The paper is focused on oxidative polymerization of aniline proceeding in an acid medium with a strong oxidant; formation of polyaniline (PANI) granular structures in different steps of the synthesis was studied. The relationship between the processes of self-organization of the growing polymer into supramolecular structures and the steps of molecular synthesis has been revealed. It was shown that during the induction period (the initial synthesis step), insoluble non-conducting products are formed. They are characterized by the absorption band at 430 nm corresponding to the wavelength of the phenazinium cation radical peak. In the second step, the polymer chain growth, conducting PANI granules with the diameter of 50 nm were obtained. These granules consist of spherical particles with the diameter as small as several nanometers. Then, the granule dimensions increased to 200 nm due to the growth of the spheres; the sphere diameter reached 20 nm. The number of spheres in a granule remained constant. Both precipitate and PANI film consist of common structural elements, polymer spheres, organized into granules and larger structures. Suppression of the polymer chain growth leads to the formation of non-conducting aniline oligomers which are self-organized into large particles with fractal structure. To describe the self-organization processes of a growing polymer chain, the diffusion-limited aggregation mechanism was used.

Polyaniline (PANI) was prepared by the oxidation of aniline hydrochloride with ammonium peroxydisulphate in water or in a water-ethanol mixture. In the presence of ethanol, PANI nanotubes and nanorods were observed. Both products were carbonised in a nitrogen atmosphere at 650°C. Initial and carbonised products were characterised by scanning and transmission electron microscopies, thermogravimetric analysis and wide-angle X-ray scattering. Their molecular structure was studied by UV-VIS, infrared, and Raman spectroscopies. Carbonised sample obtained from the PANI salt prepared in the presence of ethanol exhibits Raman spectrum which corresponds to a more ordered carbon-like material than carbonised samples obtained from the PANI base and the PANI salt prepared in pure water. The influence of ethanol present in the reaction mixture on the molecular and supra-molecular structure of PANI and, consequently, on the enhancement of chainordering of carbonised PANI is discussed.

In this paper, X-ray absorption near edge spectroscopy at the nitrogen K edge (N K XANES) data of polyaniline (PANI) and its derivatives were revisited and expanded. The N K XANES spectra of PANI nanocomposites and PANI nanofibers were also investigated. The analysis of N K XANES spectra were done by the deconvolution of bands and the 1s → π* and 1s → σ* transitions were assigned by a correlation with the N K XANES spectra of smaller organic compounds. The “free” forms of PANI were dominated by bands from 397.7 eV to 399.1 eV attributed to imine and radical cation nitrogen atoms, respectively. Nitrogen bonded to phenazine-like rings can also be seen, mainly for PANI prepared at pH higher than 3.0. The spectra of nanocomposites show sharper bands than the “free” polymers as well as new bands at 398.8 eV and 405–406 eV. These new bands were assigned to phenazine-like rings and azo bonds in the structure of the polymers (polyaniline, polybenzidine, and poly(p-phenylediamine)) within the galleries of the montmorillonite clay. PANI nanofibers doped with HCl or HClO4 show bands related to phenazine-like rings and/or dication segments of PANI, indicating that these segments are important in the formation of PANI nanofibers.

Nanostructured polyanilines of different morphologies were prepared by chemical polymerization of aniline with ammonium peroxodisulfate in aqueous HCl using various inorganic and organic chlorides as additives with the aim to determine the effect of cations of the added electrolyte on the morphology, spectroscopic characteristics, and conductivity of formed polyanilines. Chlorides of basic metals: NaCl and CaCl2 did not show any significant effect while AlCl3 and organic electrolytes were found to influence the morphology of polyanilines. The effect of organic-electrolyte additives, which actually are ionic liquids, is explained by the organization of their molecules to micellar structures that act as soft templates for emerging polyaniline nanoparticles. The effect of AlCl3 is ascribed to the transformation of its molecules to [AlCl4]− anions.

Polyaniline (PANI) was synthesized by chemical oxidation of aniline in the presence of mixtures of water-soluble poly(sulfonic acids) of different nature. Under these conditions, the use of polyacid templates leads to the formation of interpolymer complexes of PANI and polyacid mixtures. The obtained PANI complexes were characterized by UV, visible, near IR, and Fourier transform infrared spectroscopy. It was shown that the rigidity of the polyacid backbone and the composition of a polyacid mixture affect the electronic structure of PANI complexes and the duration of the induction period of aniline oxidation. Domination of the more rigid-backbone template in the synthesis of PANI complexes with mixtures of the rigid- and flexible-backbone polyacids was observed. According to the viscometry and FTIR spectroscopic data, the reason of the domination is the existence of the intermolecular interaction between the polyacids in the mixture. In this case, duration of the induction period of aniline oxidation was between these values for pure polyacids.

Changes in the various chemical and structural properties of polyaniline (PANI) films effected by interaction with Fenton’s reagent are monitored with electrochemical in situ spectroscopic and surface-sensitive techniques. Starting from a model of possible structural changes caused by chemical attack of species generated by Fenton’s reagent, particular attention is paid to the differences between the compact and highly porous (open) forms of PANI.

Photovoltaic cells composed of thin mesoporous polyaniline films sandwiched between an indium-tin oxide anode and aluminium cathode have been fabricated. The cells show an increase in the photo-generated open-circuit voltage (V oc) from 0.2 V to 0.6 V and stable-in-time V oc generation following the addition of water containing highly hydrated ions, e.g. tap water.We explain the waterpromoted photo-voltaic effect by the polarity of the water environment. Theoretical calculations show that increasing the solvent polarity increases the energy of the electronic transition related to the measured V oc. The stable-in-time V oc generation could be explained by the increase in the lifetime of the excitons as well as by their more efficient dissociation in the interpenetrating network of polyaniline and water. The penetration of water into the mesoporous polyaniline films is promoted by the presence of highly hydrated ions.

Conducting textiles of polyamide (PA) fabrics and polypyrrole (PPy) were prepared by in situ oxidative chemical polymerisation of pyrrole (Py) on the surface of PA textiles using FeCl3 as oxidant. The anionic surfactant, dodecylbenzenesulphonic acid, was used as co-dopant during Py polymerisation on the textile surface. The influence of the monomer amount and polymerisation conditions on formation of the conducting PPy layer, conductivity, morphology, and stability of the prepared PA/PPy was studied. The conductivity of modified textiles decreased rapidly after the washing process, so a special Py-functionalised silane (1-(3-(triethoxysilyl)propylamino)-3-(1-H-pyrrole-1-yl)propan-2-ol; SP) was synthesised and applied to the PA surface prior to PPy formation. The presence of SP on the PA surface after completion of the sol-gel process was verified by Fourier transform infrared spectroscopy with an attenuated total reflectance. Pyrrole polymerisation was subsequently applied to the SP pre-treated textile surface. The influence of SP concentration on both the fastness of the conducting layer after the washing process and stability of the electrical conductivity of the prepared PA/PPy samples was investigated. Surface conductivity of the samples treated and untreated by the sol-gel process of SP was measured both prior to and after washing of the prepared textiles. It was found that an application of 0.6 mass % of SP significantly improved the fastness of the PPy layers. Examination of the modified PA surface using scanning electron microscopy disclosed the differences in the formation of PPy on PA textiles when using SP and also showed differences on the PPy modified textile surface prior to and after washing. The method of X-ray photoelectron spectroscopy was used for a detailed study of the surface composition. It was confirmed that the pre-treatment with Py-functionalised triethoxysilane significantly influenced the chemical composition of the PA surface modified with PPy.

This study investigates the effect of the ionic liquid 1-butyl-3-methyl imidazolium chloride ([bmim]Cl) on the morphological, structural, and electronic properties of polyaniline (PANI) products synthesised by the falling-pH method. Products were characterised by SEM, FT-IR, UVVIS, N2-physisorption, and conductivity measurements. The [bmim]Cl addition strongly influenced the PANI morphology, specific surface area, porosity, and conductivity. Depending on the [bmim]Cl: ANI ratio and the synthesis pH, a wide range of PANI nanostructures could be prepared, with rod-like, and fibre-like elongated structures being the dominant morphology under most experimental conditions. Samples prepared in the presence of [bmim]Cl exhibit specific areas of ca 22–35 m2 g−1. The conductivity of the final products depends on the [bmim]Cl: ANI ratio. Temperature dependence of conductivity in the temperature range from 77 K to 300 K was also studied.

Poly(2-acrylamido-2-methyl-1-propanesulphonic acid) (PAMPSA)-doped polyaniline (PANI) layers are synthesised in the presence of sulphuric and perchloric acids. The effects of the inorganic acid as well as of the electrochemical synthetic procedure (potentiostatic and potentiodynamic deposition) and thickness of the polymer layers are studied. The focus is directed towards the pH dependence of the electrochemical redox activity and conductivity of the PAMPSA-doped PANI layers obtained under different conditions. Ascorbic acid oxidation is used as a test reaction to study the electrocatalytic behaviour of various PAMPSA-doped PANI layers in neutral solution. It is found that the type of inorganic component present in the polymerisation solution has a marked effect on the extent of doping in acidic solutions as well as on the redox electroactivity in neutral solutions. A comparison between potentiostatically and potentiodynamically synthesised layers at pH 7 shows a markedly lower conductance and lower extent of redox charge preservation in the case of potentiodynamic synthesis. The PANI electrocatalytic activity for ascorbic acid oxidation is also dependent on the polymer electrodeposition procedure, with potentiostatically synthesised layers exhibiting better electrocatalytic performance.

Statistical copolymers of aniline and p-phenylenediamine, poly(aniline-co-p-phenylenediamine)s, were synthesised by oxidative polymerisation using various oxidants, ammonium peroxydisulphate or silver nitrate. Depending on the choice of oxidant, copolymers or composites with silver particles were obtained. Different molar concentrations of p-phenylenediamine in the reaction mixture provided materials of different conductivities. The influence of both the copolymer composition and the presence of discrete silver particles on the electric and dielectric properties of the system was studied. The results showed a decrease in the conductivity of copolymers and their composites with the silver content compared with the content of standard polyaniline salt. The reduction in conductivity was described in terms of the decreased density of hopping centres due to defects in the copolymer structure. The dielectric relaxations observed were described in terms of their activation energies and were linked to the corresponding conduction mechanism.

A bi-hybrid composite is represented by an organic-inorganic (O-I) filler dispersed in an O-I matrix. Polyaniline-montmorillonite, as a nanocomposite filler, was synthesised by two independent processes: (1) montmorillonite was surface-modified with a conducting polymer, polyaniline, during the in-situ oxidation of aniline or (2) montmorillonite was pre-treated with aniline, then the aniline was polymerised and the polyaniline subsequently produced penetrated the montmorillonite structure. The organic-inorganic polymer matrix was formed in two independent steps: (1) inorganic building units were formed in situ by the sol-gel process, (2) followed by organic polymeric matrix formation by polyaddition reactions of epoxy groups with amines. Polyaniline-montmorillonite filler was added to the reaction system between these two steps, i.e. when the inorganic structures of the O-I matrix have already been formed but prior to formation of the organic polymeric matrix. Two different O-I matrices were prepared from functionalised organosilicon precursors and oligomeric amines. 3-[(Glycidyloxy)propyl]trimethoxysilane reacted with α,ω-oligo(propylene oxide) diamine and diethoxy[3-(glycidyloxy)propyl]-methylsilane reacted with α,ω-oligo(propylene oxide) triamine. The resulting bi-hybrid coatings, the O-I filler dispersed in the O-I matrix, were characterised by atomic-force and optical microscopies, and also by tensile tests. The filler composition affected both the mechanical and surface properties of the coatings.

Aniline was polymerised enzymatically in aqueous solution at pH = 4.3 and 25°C in the presence of submicrometer-sized vesicles formed from sodium bis(2-ethylhexyl)sulphosuccinate (AOT). H2O2 served as oxidant and the enzyme used was either horseradish peroxidase isoenzyme C (HRPC) or soybean peroxidase (SBP), both being class III peroxidases. From previous studies with HRPC, it is known that stable vesicle suspensions containing the emeraldine salt form of polyaniline (PANI-ES) can be obtained within 1–2 days with a 90–95 % yield, provided that optimal reaction conditions are applied. Unfortunately, HRPC becomes inactivated during polymerisation. In the present study, a linear dendritic block copolymer was added to HRPC, resulting in higher operational enzyme stability; the stabilising effect, however, was too small to afford a substantial decrease in the required amount of enzyme. Moreover, replacing HRPC with SBP was of no advantage, although SBP is known to be more stable towards inactivation by H2O2 than HRPC. By contrast, SBP was found to be much slower in oxidising aniline, and complete inactivation of SBP occurred before all the aniline monomers were oxidised, leading to low yields and the formation of over-oxidised products. The same was observed for HRP isoenzyme A2. Reactions without vesicles indicated that peroxidase inactivation was probably caused by PANI-ES.

In this study, polypyrrole-clay (PPy-clay) composites were prepared by the in situ chemical oxidative polymerisation of pyrrole in the presence of clay. The chemical structures of the composites were characterised by FTIR and XRD analysis. The thermal properties of these novel composites were analysed by TGA and DSC measurements. Glass-transition temperatures and char yields increased with the increase in clay content in the nanocomposites. The interactions between PPy and clay were mainly between polypyrrole and the layers of clay. It was observed that, as the amount of clay in the composites increased, the dielectric permittivity decreased while the dielectric conductivity of the composite materials increased.

Polyaniline coating was deposited on the surface of multi-wall carbon nanotubes of Russian and Taiwanese origin in situ during the polymerization of aniline. The deposited polyaniline film was subsequently carbonized under an inert atmosphere at various temperatures to produce coaxial coating of the carbon nanotubes with nitrogen-containing carbon. The new materials were investigated by infrared and Raman spectroscopies, which demonstrated the conversion of the polyaniline coating to a carbonized structure. X-ray photoelectron spectroscopy proved that the carbonized overlayer contains nitrogen atoms in various covalent bonding states. Transmission electron microscopy confirmed the coaxial structure of the composites. The Brunauer-Emmett-Teller method was used to estimate the specific surface area, the highest being 272 m2 g−1. The conductivity of 0.9–16 S cm−1 was measured by the four-point method, and it was only a little affected by the carbonization of the polyaniline coating.

Conducting poly(o-anisidine) coatings were obtained on low carbon steel in aqueous oxalic acid solution by using the galvanostatic technique. The coatings were characterised by potential-time relations, UV-VIS absorption spectroscopy, scanning electron microscopy, and X-ray diffraction measurements. The electrochemical performance of coated steel electrodes was evaluated on the basis of galvanostatic charge-discharge performance and electrochemical impedance spectroscopy in 0.5 M H2SO4. Maximum charging current was found in the case of the coating obtained at a current density of 8 mA cm−2 for 600 s duration at the supply voltage of 0.5 V. The estimated capacitance of the coated steel electrode for charging is 42.67 mF and 7.2 mF for discharging. It was also found that there was an increase in capacitance as a function of supply voltage and the maximum value was obtained at 0.5 V. The study reveals the possibility of using conducting poly(o-anisidine)-coated low carbon steel from oxalic acid medium as supercapacitor electrode materials.

The coaxial coating of multi-wall carbon nanotubes (MWCNT) with poly(aniline) (PANI) was synthesised and a paint was prepared containing conducting PANI-MWCNT composite. The corrosion protection performance was assessed by open circuit potential measurements, potentiodynamic polarisation, and electrochemical impedance spectroscopy. The corrosion rate of low-carbon steel coated with 1.5 mass % of PANI-MWCNT-based paint in 3.5 mass % sodium chloride solution was found to be 0.037 mm y−1, about 5.2 times lower than that of unpainted low-carbon steel and 3.6 times lower than that of epoxy painted steel.

Polypyrrole (PPy) is a conducting polymer which can be used for producing different ion-selective electrodes. An iodide-doped (PPy-iodide) was prepared electrochemically by anodic polymerisation of pyrrole in the presence of an iodide ion in an aqueous solution on the surface of a pencil lead. Polymerisation was investigated under galvanostatic conditions. The effects of electropolymerisation conditions on the characteristics of the potential response of the sensor were examined. Concentrations of pyrrole, iodide ions, and conditioning solution plus current density and the time of electropolymerisation were optimised in relation to the slope and linearity of calibration graphs. This electrode showed a Nernstian behaviour of 61.1 mV per decade for I− ion over a wide concentration range from 1.0 × 10−5 M to 1.0 × 10−1 M, with the limit of detection of 9.3 × 10−6 M. The response time of the electrode was from 3–5 s. The selectivity coefficients of the prepared sensors over a wide spectrum of interference anions were also evaluated, revealing that selectivity improves as a result of double-coating with PPy. A similar improvement was observed under lower current density and longer electropolymerisation time. This sensor was applied in the determination of iodide ions using titration potentiometry. This electrode can be used for the determination of iodide in drug preparations.

Two polyaniline (PANI) samples of various molecular masses were used for the preparation of palladium catalysts (with 2 mass % of Pd). The physicochemical features of starting polyanilines were found to substantially affect the size and extent of palladium nanoparticles aggregation. Strongly aggregated large palladium particles appeared in the PANI sample of more compact morphology (PANI-H), higher crystallinity and lower specific surface area. Pd nanoparticles of a definitively smaller size were formed in the more amorphous PANI sample of looser morphology (PANI-L) and the extent of particles aggregation was markedly lower. The catalytic properties of Pd/PANI samples were studied in a liquid phase hydrogenation of unsaturated triple bond (C≡C) in alkynes reactants, phenylacetylene, and cyclohexylacetylene. The 2 mass % Pd/PANI-L catalyst prepared using polymer of less compact texture exhibited much higher activity in both reactions. In the presence of the 2 mass % Pd/PANI-L catalyst, alkene products were formed with a high selectivity (approximately 90 %) attained at the almost complete conversion of alkynes. This highly selective hydrogenation of the C≡C to the C=C bond was related to the presence of an electroactive polymer, PANI, in close proximity with Pd active sites. Polyaniline could have a role in a steric effect as well as in a modification of adsorptive properties of Pd centres.

An approach for improving the power generation of a dual-chamber microbial fuel cell by using a nanostructured polyaniline (PANI)-modified glassy carbon anode was investigated. Modification of the glassy carbon anode was achieved by the electrochemical polymerisation of aniline in 1 M H2SO4 solution. The MFC reactor showed power densities of 0.082 mW cm−2 and 0.031 mW cm−2 for the nano- and microstructured PANI anode, respectively. The results from electron microscopy scanning confirmed formation of the nanostructured PANI film on the anode surface and the results from electrochemical experiments confirmed that the electrochemical activity of the anode was significantly enhanced after modification by nanostructured PANI. Electrochemical impedance spectroscopic results proved that the charge transfer would be facilitated after anode modification with nanostructured PANI.

In situ polymerised thin polyaniline (PANI) films produced on polystyrene dishes were tested for their antibacterial activity with respect to Escherichia coli and Staphylococcus aureus, representing both gram-positive and gram-negative bacteria. PANI films were subsequently used for the reduction of silver ions to metallic Ag. PANI salt and base in original forms and after the deposition of Ag were studied. PANI salt showed a significant antibacterial effect against both bacteria strains while the efficacy of neat PANI base was only marginal. After the Ag deposition, the PANI base exhibited different levels of antibacterial effect depending on the type of the bacterial strain; the growth of gram-positive Staphylococcus aureus was inhibited depending on the Ag concentration on the film, while Escherichia coli remained uninfluenced. Efficacy of the PANI salt with deposited Ag against both bacteria strains was comparable with that of PANI alone and was not affected by the Ag concentration. The results show that Ag deposition can be a suitable method for the preparation of PANI base films with improved antibacterial properties.

While conductivity and other electrical properties are key parameters in the design of polymer electronics, equally important mechanical properties of conducting polymers have rarely been reported. The influence of preparation conditions of polyaniline pellets on mechanical and electrical properties was therefore studied. Conductivity of polyaniline is commonly measured using pellets prepared by the compression of powder. It is shown that a pressure of at least 300 MPa is needed to obtain a reliable value of conductivity. At lower pressures, the samples have lower apparent conductivity, density, Young modulus, and hardness. Above the compression limit of 300 MPa, these parameters become constant, except for the density. The same behavior was observed both for conducting polyaniline hydrochloride and for the non-conducting polyaniline base. The puzzling observation that density of the pellets decreased as the compression pressure increased is discussed considering the relaxation processes.