Core–shell structured and electro-magnetic functionalized polyaniline composites

Core–shell structured and electro-magnetic functionalized polyaniline (PANI) composites were chemically prepared by micro-spherical hydroxyl iron (Fe(OH)) magnet as the hard-template associated with a self-assembly process in the presence of β-naphthalene sulfonic acid (β-NSA) as the dopant. Field emitting scanning electron microscope (SEM) and transmission electron microscope (TEM) measurements indicate that the electro-magnetic functionalized PANI–β-NSA/Fe(OH) composites have a novel core–shell structure, in which micro-spherical Fe(OH) magnet (0.5–5 μm in diameter) is as the core, and self-assembled PANI–β-NSA nanofibers (30–50 nm in diameter) formed on the surface of the Fe(OH) microspheres is as the shell (60 nm in thickness). Moreover, the electro-magnetic properties of the core–shell micro/nanostructured composites are adjustable by changing the ratio of Fe(OH) to aniline monomer.     

Large-area network of polyaniline nanowires supported platinum nanocatalysts for methanol oxidation

Nanocomposites comprised of Pt nanoparticles and electrically conducting polymers were prepared and tested for the electrocatalytic performance towards oxidation of methanol. Films of polyaniline (PANI) synthesized independently by potentiostatic and galvanostatic method, PANI(V) and PANI(I), respectively, were used as the supporting matrix for loading Pt nanoparticles. PANI(V), PANI(I), PANI(V)/Pt, and PANI(I)/Pt films were characterized for structure and morphology using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). SEM image of PANI(I) reveals that the particles are highly porous and interconnected nanowires, whilst PANI(V) particles are granular. The large surface area in the nanofibrillar PANI(I) makes the dispersion of Pt particle with a lesser time for the deposition of Pt particles. The porous network structure of PANI(I) helps in effective dispersion of Pt particles (about 10–20 nm) and facilitates easy access of methanol to the catalytic sites. The electrocatalytic activity of PANI(I)/Pt is much higher (current density (24.7 mA/cm² mg) at 0.68 V) in comparison to PANI(V)/Pt and bulk Pt electrodes (the current density values of 5.5 and 7.5 mA/cm² mg).     

Photoinduced protonation of polyaniline assisted by hydrogen-bonding materials

Composites of the emeraldine base form of polyaniline (PANI-EB) and photo-acid generators (PAGs) increase their conductivities upon photo-irradiation due to protonation of PANI-EB. Such materials may be utilized to fabricate conducting patterns by photo-irradiation. However, the conductivity obtained by direct irradiation of PANI-EB/PAG composites was normally quite low, and conductivity above 10^?3 S cm^?1 often required post-treatment with HCl. In this work, poly(vinyl alcohol) (PVA), which can form a hydrogen bonding network, was added to PANI-EB/PAG. Results showed that PVA enhanced film quality, conductivity and reproducibility. Photo-induced conductivity of 10^?2 S cm^?1 was obtained when the ratio of PANI-EB/PVA/PAG was 1:1:0.6. A novel PAG, bis(p-hydroxyphenyl)phenylsulfoniumtriflate [(PhOH)₂PhS⁺ OTf^?], which can form hydrogen bonds with PANI was synthesized and mixed with PANI-EB. A composite of PANI-EB and the PAG with a ratio of 1:0.5 achieved a conductivity of 10^?1 S cm^?1 after irradiation. However, the initial conductivity before irradiation was as high as 10^?5 S cm^?1 due to relatively high acidity of the PAG.     

In-situ electrochemical polymerization of multi-walled carbon nanotube/polyaniline composite films for electrochemical supercapacitors

Multi-walled carbon nanotube (MWCNT)/polyaniline (PANI) composite films were prepared by in-situ electrochemical polymerization of an aniline solution containing different MWCNT contents. The supercapacitive behaviors of these films were investigated with cyclic voltammetry (CV), charge–discharge tests, and ac impedance spectroscopy. The results revealed that the MWCNT/PANI films show much higher specific capacitance (SC), better power characteristic, better cyclic stability, and more promising for applications in supercapacitors than a pure PANI film electrode. The highest specific capacitance value of 500 F g^?1 was obtained for the MWCNT/PANI composite film containing MWCNT of 0.8 wt.%. The improvement mechanisms of the capacitance of the composites are also discussed in detail.     

Preparation and electrical properties of highly (1 1 1) oriented antiferroelectric PLZST films by radio frequency magnetron sputtering

Highly (1 1 1) oriented lead lanthanum zirconate stannate titanate (PLZST) films were synthesized on Pt/Ti/SiO₂/Si substrates by radio frequency (RF) magnetron sputtering. The microstructure and electrical properties of the films were investigated as a function of post-annealing temperature. Smooth and crack-free films obtained by post-annealing at 700 °C for 30 min, and exhibit a dense columnar microstructure with a grain size of ∼0.85 μm. The sputtered PLZST films of nominal composition Pb_0.97La_0.02 (Zr_0.60Sn_0.30Ti_0.10)O₃ display a high saturation polarization of ∼70 μC cm⁻², a low antiferroelectric-to-ferroelectric switching field (<100 kV cm⁻¹), a reasonable dielectric constant and a low loss tangent. This combination of properties makes them attractive for microdevice applications.     

Kinetic study of the electrochemical degradation of polyaniline

The kinetics of the electrochemical degradation of polyaniline (PANI) layers, deposited by electropolymerization and chemical polymerization onto platinum electrode, was investigated in an acid aqueous solution. The degradation rate was shown to depend greatly on the electrode potential applied. First-order rate constants of degradation, obtained from the kinetic data, were shown to vary between 2.87×10⁻⁵ and 3.11×10⁻³ s⁻¹ for thick PANI films, having the electrochemical charge density of 14 mC/cm², and between 2.0×10⁻⁵ and 3.60×10⁻³ s⁻¹ for thin PANI films, having the charge density of 1.5 mC/cm², within the electrode potential range of 0.3–0.9 V versus Ag/AgCl. Two linear regions were found to present on the dependencies of logarithm of the first-order degradation rate constant on electrode potential, one of them having a slope of 0.44 and 1.34 V⁻¹ within electrode potential limits of 0.3–0.6 V, and another one having a slope of 6.37 and 6.39 V⁻¹ within potential limits of 0.6–0.9 V, for thick and thin polymer films, respectively. The results obtained show that the electrochemical degradation of PANI films proceed at a remarkable rate even at low electrode potential values.     

The reduction of silver nitrate to metallic silver inside polyaniline nanotubes and on oligoaniline microspheres

Polyaniline (PANI) reduces silver nitrate to metallic silver. Composites based on conducting polymer and silver have been prepared with equimolar proportions of reactants. Polyaniline bases having different morphologies – granular or nanotubular – and oligoaniline microspheres have been left to react with silver nitrate in acidic, neutral, and alkaline media. The content of silver, typically 20–30 wt.%, was determined by thermogravimetric analysis. Clusters of 40–80 nm silver particles are produced in the granular form of PANI. The formation of silver inside PANI nanotubes has been observed. With oligoaniline microspheres, silver was produced on their surface, and on PANI agglomerates accompanying them. The highest conductivity, 943 S cm^?1, was found with silver reduced by nanotubular PANI base in 0.1 M nitric acid at 17.3 wt.% silver content. The standard granular PANI, used as a reference material, yielded a composite having a much lower conductivity of 8.3 × 10^?5 S cm^?1 at 24.3 wt.% Ag. There is no simple correlation between the conductivity and silver content. Infrared and Raman spectroscopies have been used to study the changes in the molecular structure of the PANI bases of various morphologies before and after reaction with silver nitrate.     

Stable polyaniline dispersions prepared in nonaqueous medium: synthesis and characterization

Peroxodisulfate-induced polymerization of aniline at 10°C in acidic (HCl) nonaqueous medium using dimethyl sulfoxide (DMSO) as the solvent, readily produced polyaniline (PANI) in a stable dispersion form. The stability of the dispersion of PANI in the nonaqueous (DMSO) medium is much enhanced when the same is synthesized in the presence of a support polymer, poly(vinyl alcohol) (PVA) dissolved in the solvent. Results of studies on HCl-doped PANI prepared in DMSO medium by UV–VIS and FTIR spectroscopy support that the doped PANI so obtained is structurally similar to that of doped PANI prepared likewise in acidic aqueous medium. PANI and PANI–PVA composite as prepared in DMSO medium and the relevant isolated dry products were further characterized thermally, employing differential scanning calorimetry (DSC) and thermogravimetry (TG) and morphologically, employing transmission electron microscopy (TEM). HCl-doped PANI prepared separately in DMSO and aqueous media shows electrical conductivity values of 1.07 and 12.0 S cm⁻¹, respectively, the polymer prepared in nonaqueous medium (DMSO) being measurably poorer in electrical conductivity,     

Preparation of porous nanorod polyaniline film and its high electrochemical capacitance performance

Nano-sized polyaniline (PANI) films were electrochemically deposited onto an ITO substrate by a pulse galvanostatic method (PGM) in an aqueous solution. The morphology of the as-prepared PANI film was characterized using a field emission scanning electron microscope (FESEM). It was observed that the as-prepared PANI films were highly porous, and showed a nano-sized rod-like or coralline-like morphology depending on the charge loading performed in the electropolymerization process. Furthermore, the PANI films were electrochemically measured by the galvanostatic charge–discharge (GCD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests in 1 mol L^?1 HClO₄ solution. The results showed that such PANI films had a favorable electrochemical activity and an excellent capacitance. The rod-like PANI film prepared with the charge loading of 1000 mC showed the highest discharge capacitance of 569.1 F g^?1 at a low current density of 1 A g^?1. The discharge capacitance retained 97.7% after 1000 cycles at a large current density of 10 A g^?1.     

The manufacture and properties of polyaniline nano-films prepared through vapor-phase polymerization

We succeeded in the chemical preparation of nano-level thick polyaniline (PANI) emeraldine salt films on plastic substrate by an in situ vapor-phase deposition (VDP) polymerization method under ambient conditions, using a self-assembly method which is unprecedented. Homogeneous conductive PANI thin films were uniformly fabricated at nano-level thickness (20–100 nm), but their morphologies could grow as polycrystalline grains of a highly ordered structure, depending on the deposition conditions. The grain size was also controlled between 30 and 100 μm depending on the deposition time/temperature. The surface resistance of PANI films was enhanced up to 10⁴ Ω/square with crystallization and light transmittance was increased up to 90% in the case of a film less than 30 nm thick. A typical spectrum for the oxidized PANI, the emeraldine salts form, showing π–π^* transition and a polaron lattice were observed by UV–visible/IR and infrared /Raman spectroscopy.     

Spectroscopic investigation of the interactions between emeraldine base polyaniline and Eu(III) ions

The interactions of emeraldine base form of polyaniline (EB-PANI) and Eu(III) ions in 1-methyl-2-pyrrolidinone (NMP) solution and in films have been investigated by UV–vis–NIR, resonance Raman, luminescence and electron paramagnetic resonance (EPR) spectroscopies. These spectroscopic techniques allowed to characterize quinone and semiquinone segments in the polymeric chains, and the oxidation state of europium ions in Eu-PANI samples. For high values of Eu(III)/N molar ratio (24/1) the presence of a weak polaronic absorption band at 980 nm in UV–vis–NIR spectrum and the observation of bands at 1330 and 1378 (ν_C–N+) cm^?1 due to emeraldine salt in the Raman spectrum at 1064 nm indicate a low doping degree. Oxidation of EB-PANI to pernigraniline base (PB-PANI) occurs in diluted solutions. The experimental data showed that the solvent plays an important role on the nature of formed species. The narrow EPR signal at g = 2.006 (line width 8G) confirms the presence of PANI radical cations in Eu-PANI film. The absence of broad signal characteristic of Eu(II) in EPR spectrum suggested that europium ions are primarily at Eu(III) oxidation state. The luminescence spectra of Eu-PANI film presented emission bands at 405 and 418 nm assigned to PANI moieties and bands at 594, 615 and 701 nm assigned to ⁵D₀ → ⁷F_J (J = 1, 2 and 4, respectively) transitions of Eu(III). EPR and photoluminescence data confirm that europium ions are mainly in Eu(III) oxidation state in Eu(III)/PANI films.     

Preparation of organo-soluble polyanilines in ionic liquid

A method for preparation of organo-soluble polyaniline (PANI) is described. Oxidative coupling polymerization of anilium chloride with ammonium persulfate in a new ionic liquid, 2-hydroxyethyl ammonium formate (HAF), gives organo-soluble polyaniline with appreciable molecular weights (M_w = 86,400). Interestingly polyaniline (PANI) prepared by this method is highly soluble in many organic solvents such as acetone, tetrahydrofurane, dioxane, dimethyformamide and N-methyl, 2-pyrrolidinone. Thin films of PANI prepared at 0 °C (by solvent casting) show reasonable conductivities (up to 37.0 S cm⁻¹) when doped with p-toluene sulfonic acid.     

Alkali doped poly(vinyl alcohol) for potential fuel cell applications

Optical transparent, chemically stable alkaline solid polymer electrolyte membranes were prepared by incorporation KOH in poly(vinyl alcohol) (PVA). The distributions of oxygen and potassium in the membrane were characterized by XRD and SEM–EDX. It is demonstrated that combined KOH molecules may exist in the PVA matrix, which allow it to be an ionic conductor. In particular, the chemical and thermal stabilities were investigated by measuring changes of ionic conductivities after conditioned the membrane in various alkaline concentrations at elevated temperatures for 24 h for potential use in fuel cells. The membranes were found very stable even in 10 M KOH solution up to 80 °C without losing any membrane integrity and ionic conductivity due to high dense chemical cross-linking in PVA structure. The measured ionic conductivity of the membrane by AC impedance technique ranged from 2.75 × 10^?4 S cm^?1 to 4.73 × 10^?4 S cm^?1 at room temperature, which was greatly increased to 9.77 × 10^?4 S cm^?1 after high temperature conditioning at 80 °C. Although, a relatively higher water uptake, the methanol uptake of this membrane was one-half of Nafon 115 at room temperature and 6 times lower than that of Nafion 115 after conditioned at 80 °C. The membrane electrolyte assembly (MEA) fabricated with PVA–KOH in direct methanol fuel cell (DMFC) mode showed an initial power density of 6.04 mW cm^?2 at 60 °C and increased to 10.21 mW cm^?2 at 90 °C.     

Electrosynthesis of polyaniline films on titanium by pulse potentiostatic method

Polyaniline (PANI) was synthesized on titanium electrode from aqueous solution containing 0.3 mol L⁻¹ aniline and 1 mol L⁻¹ HNO₃ by pulse potentiostatic method. The chronoamperogram during polymerization process of aniline was recorded. The effects of the synthesis parameters, such as anodic pulse duration (t_a), cathodic pulse duration (t_c), lower limit potential (E_c) and upper limit potential (E_a), on the morphology and electroactivity of the PANI films were investigated by scanning electron microscopy (SEM) and cyclic voltammetry (CV). SEM results present that flake, mica-like, quasi-fibrous and nano-fibrous PANI film could be synthesized with various polymerization parameters. Under the following conditions, t_a = 0.8 s, t_c = 0.1 s, E_c = 0 V and E_a = 1.0 V, high quality nano-fibrous PANI film with the best electroactivity was obtained. The CV results show that the PANI films with different morphologies, which were prepared under the same anodic polymerization charge, have obvious different characteristics. This means that the PANI films with different morphologies have different electrochemical activity.     

The carbonization of granular polyaniline to produce nitrogen-containing carbon

Polyaniline (PANI) was prepared by the oxidative polymerization of aniline. The deprotonated product, a PANI base, was carbonized in an inert atmosphere at temperatures up to 800 °C for various times. The mass decreased to 40–50 wt.% at temperatures above 600 °C. The progress of molecular structure during carbonization was followed by infrared and Raman spectroscopies. The carbonization at 650 °C for 1 h is suggested for the optimum conversion of PANI to carbon. The product retained the original globular structure of PANI. The conductivity of the carbonized material was low for carbonizations below 600 °C, <10^?10 S cm^?1, and increased to 10^?4 S cm^?1 after treatment at 800 °C. The content of nitrogen, ～10 wt.%, was not affected appreciably by the carbonization.     

Investigation of electrical properties of nanostructured carbon films derived from block copolymers

Electrical properties of nanostructured carbon (ns-C) films fabricated by pyrolysis of PAN–b–PBA copolymers were investigated. Films having cylindrical morphology and pyrolyzed at 400, 500 and 600 °C were investigated. Both carbide forming (Zr, Ti) and non-carbide forming (Cu, Pt) metals spanning a wide range of electron work functions (4.1–5.5 eV) formed ohmic contacts to the ns-C films in the as-deposited state. The conductivity of the ns-C films increased roughly three orders of magnitude for every 100 °C increase in the pyrolysis temperature. Hall-effect measurements showed that the films pyrolyzed at 600 °C were n-type with a majority carrier concentration and mobility of 5.8 × 10¹⁸ cm^?3 and 0.97 cm²/V s, respectively. Current–voltage measurements as a function of temperature (I–V–T) were performed on films pyrolyzed at 600 °C, whereas films pyrolyzed at 400 and 500 °C were too resistive for reliable resistivity–temperature and Hall-effect measurements. The resistivity as a function of temperature was analyzed by using the reduced activation energy method and was determined to follow variable-range hopping (VRH) mechanisms at and below room temperature. The data indicates a crossover from Efros–Shklovskii VRH [J. Phys. C 8, (1975) L49] to Mott VRH [J. Non-Cryst. Solids 1, (1968) 1] at temperatures above 100 K.     

Synthesis and characterization of polyaniline–Fe3O4 nanocomposite: Electrical conductivity,magnetic, electrochemical studies

Fe₃O₄ nanoparticles were prepared by hydrolysis reaction of urea in ethylene glycol as solvent at 160 °C. The prepared Fe₃O₄ nanoparticles were incorporated into polyaniline (PANI) matrix during in situ chemical oxidative polymerization of aniline with different molar ratios of aniline:Fe₃O₄ (19:1, 16:1, 12:1, 9:1) using (NH₄)₂S₂O₈ as oxidant in aqueous solution of sodium dodecylbenzene sulphonic acid under N₂ atmosphere. Room temperature conductivities of the synthesized PANI, PANI/Fe₃O₄ (19:1) and PANI/Fe₃O₄ (9:1) are 3.2 × 10^?4, 1.8 × 10^?5 and 1.0 × 10^?5 S/cm, respectively, indicating decrease of conductivity with increase of Fe₃O₄ in PANI. Saturation magnetizations of Fe₃O₄, PANI/Fe₃O₄ (19:1), and PANI/Fe₃O₄ (9:1) are 27.5, 5.5 and 6.3 emu/g, respectively, indicating an increase of ferromagnetic interaction with more incorporation of Fe₃O₄ in PANI matrix, whereas PANI is diamagnetic. Electrochemical studies shows that Zn-PANI/Fe₃O₄ (9:1) battery had delivered maximum discharge capacity (78.6 mAh/g) as compared to Zn-PANI battery (50.1 mAh/g) at constant current of 0.5 mA cm^?2. At constant resistance of 1000 Ω, discharge capacities of Zn-PANI/Fe₃O₄ and Zn-PANI battery are 73.37 and 50.8 mAh/g, respectively.     

Microwave study of chemically synthesized conducting polyaniline on alumina

Polyaniline (PANI) thin film on alumina was prepared by the chemical oxidation of aniline with ammonium peroxydisulphate in acidic aqueous medium. DC conductivity, microwave transmission and reflection, microwave conductivity, shielding effectiveness and microwave dielectric constant of the conducting PANI films are reported. DC conductivity was between 0.15 × 10^?3 and 3.13 × 10^?3 S/cm. Microwave conductivity was between 0.2 and 10 S/cm. The PANI films coated on alumina gave shielding effectiveness value of ?1 to ?4 db. The ?′ was between 2 and 350 whereas ?″ was between 437 and 60. Measurements have been carried over the frequency range of 8.2–18 GHz.     

Enhanced field emission from polyaniline nano-porous thin films on PET substrate

Conducting polyaniline (PANI) nano-porous film synthesized on PET substrate by vapor deposition technique has shown excellent field emission behaviour and the emission was further enhanced by conditioning with vacuum electric discharge. Detailed study on the field emission for PANI films synthesized with different oxidant concentration was performed. Measurement was also carried out for different anode-sample separation. Turn-on field as low as 0.5 V/μm and emission current density as high as 20.96 mA/cm² was observed. The field enhancement factors were found to be in the range of 1192–3782. The films were characterized with X-ray diffraction, UV–vis spectroscopy, Fourier transformed infrared spectroscopy, scanning electron microscopy and also atomic force microscopy. The synthesized PANI films may be a promising material for field emission devices and also for plastic display industry.     

Electrochemical synthesis and corrosion behavior of polyaniline-benzoate coating on copper

Electrochemical polymerization of polyaniline (PANI) coating on copper electrode was performed galvanostatically in the current density range between 0.50 and 1.25 mA cm^?2, from aqueous solution of 0.3 mol dm^?3 sodium benzoate and 0.2 mol dm^?3 aniline. The corrosion behavior of PANI coated copper and copper electrode exposed to 0.5 mol dm^?3 sodium chloride solution was investigated by potentiodynamic and electrochemical impedance spectroscopy techniques. It was observed that thin PANI (5 μm) coating had provided efficient protection (～96%) to copper in 0.5 mol dm^?3 sodium chloride solution. Unusual initial impedance behavior to that normally observed with conventional organic coatings was attributed to dedoping of benzoate anions from the polymer coating.