Intercalation of Polyaniline in Montmorillonite and Zeolite

The anilinium ion was encapsulated into the interlayer space of montmorillonite and the intrachannel space of NaY zeolite by the ion exchange method. After addition of ammonium peroxodisulfate, the loaded anilinium ions were polymerized to polyaniline (PAN). The structures of PAN in NaM and CsM are compared with that in NaY by means of UV-Vis, FTIR and EPR spectroscopies. The structures of PAN in NaY zeolite and montmorillonite hosts were shown to have the typical spectral features of emeraldine base and emeraldine salt respectively. Intercalation of polyaniline in montmorillonite was confirmed by the variation of the basal spacing, the resonances in EPR and the reduction of bulk conductivity.     

Removal of toxic hexavalent chromium by polyaniline modified clinoptilolite nanoparticles

In this work clinoptilolite nanoparticles were modified with conducting polyaniline by the polymerization of anilinium cations in and out side of the clinoptilolite channels and a nanocomposite of polyaniline/clinoptilolite was obtained. Cations (Na⁺, K⁺, Mg²⁺, Ca²⁺...) in the natural clinoptilolite structure were exchanged with anilinium cations by the treatment of clinoptilolite nanoparticles in an acidic solution of aniline monomer. The cation exchange process was confirmed by elemental analysis of nitrogen and carbon atoms of anilinium cations in clinoptilolite dry powder after treatment. The polyaniline/clinoptilolite nanocomposite was obtained by the oxidative polymerization of anilinium cations within the clinoptilolite structure. The polyaniline/clinoptilolite nanocomposite was characterized utilizing FT-IR and X-ray diffraction measurements and was used for the removal of Cr(VI) from aqueous solutions in chromate anion form as an important water pollutant. The effect of a number of parameters such as initial concentration of Cr(VI), amount of nanocomposite and contact time on the removal efficiency of Cr(VI) by polyaniline/clinoptilolite nanocomposite were determined and optimized. It was found that after 5 min of exposure of nanocomposite powder with Cr(VI) solutions in the concentration range of 25 to 100 ppm, more than 98% of chromate anions can be removed and the Cr(VI) removal capacity per one gram of nanocomposite is about 0.3 mmol of Cr(VI).     

Raman study of PANI thin film during long time period in dependence on storage conditions

Conducting polymer polyaniline which is nowadays in forefront of the interest was in our study prepared in a form of thin films from anilinium sulfate by its chemical oxidation using ammonium peroxydisulfate. During the oxidation process, the polyaniline was deposited on glass slides and immersed into reaction mixture. Two sets of polyaniline thin films were prepared with different oxidation times (10, 20, 30, and 40 min). The first set was kept dry in desiccator and the second one was freely exposed to air moisture. Raman spectroscopy, nondestructive technique which is very sensitive to changes in structure of polymers, was used for the characterization of the protonation state of prepared polyaniline thin films. It was found that storage conditions affect the protonation state which in case of samples kept in desiccator is maintained without significant changes for longer time. Raman spectroscopy also revealed the dependence of protonation state on the oxidation time and 10 min proved as not sufficient for the creation of the protonation form of polyaniline.     

Polymerization of anilinium–DBSA in the presence of clay particles: kinetics and formation of core‐shell structures

This paper is an extension of previous work on polymerization of anilinium–DBSA (dodecylbenzenesulfonic acid) in an aqueous dispersion in the presence of mica or talc silicate particles. The presence of mica or talc particles greatly accelerates the polymerization process of anilinium‐DBSA and an encapsulated structure is formed as well. The catalytic effect of various metallic cations which exist in the chemical compositions of mica or talc on the polymerization kinetics of anilinium‐DBSA was investigated. The conductivity results along with microscopy observations prove a well formed encapsulated structure for the polyaniline/mica composites, but less for the polyaniline/talc composites. The anilinium‐DBSA complex and mica aqueous dispersions pretreated at different temperatures prior to polymerization have shown a significant effect on the polymerization rate of anilinium‐DBSA. The higher the dispersion temperature, the higher is the polymerization rate found. Copyright © 2001 John Wiley & Sons, Ltd.     

Electrochemical behavior of MF-4SK/polyaniline composites as investigated by membrane voltammetry

Membrane voltammetry was used to investigate composites consisting of perfluorinated MF-4SK membranes and polyaniline (PANI) and synthesized under various conditions. A theoretical analysis of the influence of transport-structure parameters of the ion-exchange membranes on their selectivity and limiting-current value is carried out. For MF-4SK/PANI composites, the increase in the exchange potential at the overlimiting state is found to be more than 2V compared to the original membrane. An analysis of how various factors influence the parameters of a current-voltage curve shows that the presence of anilinium and Fe³⁺ ions in the electromembrane system has no effect on the value of the potential at the onset of the overlimiting state. A phenomenological model is proposed to account for the increased plateau length at the limiting current through a change in the energetic state of water in the perfluorinated-membrane matrix resulting from the template synthesis of polyaniline.     

Polyoxometallates as inorganic templates for monolayers and multilayers of ultrathin polyaniline

The ability of a polyoxometallate (dodecamolybdophosphate) to form negatively charged monolayers on solid electrode surfaces is explored here to perform immobilization of monomeric (anilinium) units followed by electropolymerization within the monolayer. Consequently, hybrid films containing ultrathin conducting polymer (polyaniline) layers can be formed. By repeated and alternate treatments in solutions of dodecamolybdophosphate anions and anilinium cations, the amount of the material can be increased systematically in a controlled fashion leading to stable three-dimensional multilayer hybrid assemblies. The fact, that formal potentials of the dodecamolybdophosphate redox processes appear in the potential range where polyaniline is conductive, allows the system to operate reversibly and reproducibly in acid electrolyte.     

Synthesis of core-shell composites using an inverse surfmer

Anilinium dodecylsulfate was prepared from aniline and sodium dodecylsulfate. The critical micellar concentration of the salt was determined using electrical conductimetry, which revealed that the change of countercation, sodium by anilinium, reduced the critical micellar concentration with respect to the conventional counterpart, sodium dodecylsulfate. The anilinium dodecylsulfate was used as the surfmer in the synthesis of polystyrene/polyaniline core-shell composites, first performing as the surfactant to stabilize the emulsion polymerization of styrene, and later as the monomer to synthesize polyaniline via oxidative polymerization. Here, the surfmer function was directed toward the external phase instead of to the internal phase, as with conventional surfmers with carbon-carbon double bonds. Consequently, the term inverse surfmer is proposed. Analyses of its composite microstructure using electron microscopy and thermogravimetric analysis confirmed the core-shell arrangement.     

Solvent free synthesis of polyaniline-clay nanocomposites from mechanochemically intercalated anilinium fluoride

Nanocomposites consisting of conducting polyaniline and clay minerals were successfully synthesized from mechanochemically intercalated anilinium fluoride; the nanocomposites prepared by the mechanochemical intercalation method contained much more polyaniline in the clay layers than those prepared by a conventional solution method.     

An infrared and Raman spectroscopic study of polyanilines co-doped with metal ions and H+

Polyanilines doped with (HCl+KCl) and (HCl+CoCl2) were prepared by co-doping method, respectively. For comparison, polyaniline emeraldine salt (ES) by doping with HCl and its emeraldine base (EB) form were also synthesized. The co-doped polyanilines, ES and EB samples were all characterized by Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy aiming to understand the transformations in the different doping status. The results show that the doping degree of K+ ions is considerably higher than that of Co2+ ions under the same co-doping conditions possibly due to different pseudoprotonation constants of EB with K+ ions and Co2+ ions. Moreover, morphology difference of polyaniline co-doped with alkaline metal ions or transition meal ions may arise from different coordination geometry of metal ions. Nevertheless, there are similar chemical transformations of quinoid units to benzenoid ones on polyaniline backbones for the ES and both co-doped samples. And the polyaniline backbones co-doped with H+ and metal cations are found to attain weaker charge delocalization than the ES which is doped solely with H+.     

Anilinium 5-sulfosalicylate electropolymerization on mild steel from an aqueous solution of sodium 5-sulfosalicylate/disodium 5-sulfosalicylate

Aniline is electropolymerized on bare and chemically pretreated mild steel from an aqueous solution of 0.10 M anilinium 5-sulfosalicylate in 0.20 M sodium 5-sulfosalicylate/0.20 M disodium 5-sulfosalicylate buffer as the supporting electrolyte, at room temperature. At constant anodic potential black poly(anilinium 5-sulfosalicylate) (PANISSA) films are obtained on bare mild steel and characterized by IR spectroscopy, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). IR spectroscopic analysis confirms typical polyaniline structure with 1,4-disubstituted aromatic nuclei and incorporation of sulfosalicylate anions as dopants. Adhesion of PANISSA films is significantly improved when the mild steel electrode surface is chemically pretreated by 0.10 M ammonium peroxydisulfate aqueous solution. The IR spectra of the films obtained on chemically pretreated mild steel surface indicate an interaction between PANISSA and products of the mild steel oxidation by peroxydisulfate. The SEM images show differences in morphology between PANISSA films synthesized on bare and chemically pretreated mild steel surface. The efficient anticorrosion behavior of adherent PANISSA film on chemically pretreated mild steel is proved by EIS. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 12, pp. 1497–1504. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes.” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

Immobilization of phthalocyanines in conducting polymers. Polyaniline-copper tetrasulfophthalocyanine

Interaction between the anilinium cation and copper tetrasulfophthalocyanine anion (CuTSPc) was studied in an aqueous sulfuric acid solution using electronic absorption spectra. It was shown that up to 0.15 M aniline could be introduced into the solution at the dye concentration of 10⁻³ M, after which a solid deposit of a complex (salt) between the anilinium cation and copper tetrasulfophthalocyanine anion started precipitating rapidly. The effect of the dye on the kinetics of aniline polymerization on conducting glasses and on the properties of the polymer obtained was studied. It was found that phthalocyanine accelerates electropolymerization of aniline and is immobilized within the polymer matrix. It was shown that the self-catalytic synthesis mechanism characteristic of polyaniline is also preserved in the case of the composite of polyaniline-copper tetrasulfophthalocyanine.     

Growth of ramification-like ZnO rods in the presence of polyaniline

To obtain new materials with synergetic or complementary behaviors, polyaniline composite filled with ZnO rods in ramification-like structure was prepared by a hydrothermal approach. Comparative experiments of ZnO preparation in the presence of some metal ions were also carried out. The results indicated that the morphology of ZnO was strongly affected by the preparation condition. The method to grow ZnO rods in the presence of polyaniline offers a simple approach to obtain polyaniline composite filled with linear ZnO structure. The results of X-ray photoelectron spectroscopy show that the strong interaction between ZnO and polyaniline possibly exists to cause the charge transfer.     

Preparation of Nanosized Metallic Particles in Polyaniline

The preparation of nanosized gold and palladium particles in polyaniline has been carried out via the reduction of AuCl(3) or Pd(NO(3))(2) by polyaniline in either aqueous media or N-methylpyrrolidinone (NMP). When the reduction of AuCl(3) was carried out in NMP solutions of polyaniline, the Au particles were on the order of 20 nm. The reduction of AuCl(3) or Pd(NO(3))(2) by polyaniline in the powder form in aqueous media resulted in the accumulation of the elemental Au or Pd on the surface of the polyaniline particles. Subsequent dissolution of the polyaniline in NMP resulted in metal particles of about 50 to 200 nm being dispersed in the NMP solution of polyaniline. The rate of metal salt reduction and the size of the metal particles were found to be strongly dependent on the medium used, the initial ratio of metal ions to polyaniline, and the reaction time. The polyaniline-metal particle systems were characterized using X-ray photoelectron spectroscopy, UV-visible absorption spectroscopy, and FTIR spectroscopy. Scanning and transmission electron microscopy and laser light scattering were used to determine the size of the metal particles in polyaniline. Copyright 2001 Academic Press.     

Facile one‐pot synthesis and characterization of novel nanostructured organic dispersible polyaniline

Novel polyaniline (PANI) with nanotube, nanosheet, and nanofiber shapes was facilely synthesized by a self‐templating one‐pot process. Anilinium‐dodecylsulfate (DS) complex, obtained by mixing equivalent amounts of aniline and sodium dodecylsulfate (SDS), played a template‐like role in forming PANI nanostructures. It was found that the morphology and electrical conductivity of the PANI nanostructures changed with the amount of SDS and the reaction temperature. Nanotube‐shaped PANI synthesized at the temperature of anilinium‐DS complex formation in presence of SDS (concentration <0.12 M) showed high conductivity (12.9 S/cm). At higher temperature, the morphology changed to shape of a rose flower and electrical conductivity decreased to 3.95 S/cm. This suggested that both temperature and SDS concentration were key parameters for controlling the formation of the anilinium‐DS complex that acted as a template. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1024–1029, 2009     

Barrier effects of polyaniline layer in surface modified MF-4SK/Polyaniline membranes

An express method of synthesis of surface-modified membrane composites is suggested that allows obtaining heterogeneous materials featuring effects of the blocking of the transport of solvent ions and molecules. Studies using the methods of atomic force microscopy (AFM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and IR spectroscopy show that polyaniline is in the form of emeraldine and water at the interface of polyaniline aromatic chains and initial membrane sulfogroups is in a structured state due to formation of interpolymer complexes. This determines higher thermal stability of composites and specific morphology of the polyaniline layer. Measurement of electroosmotic and diffusion permeability and also membrane conductivity in HCl solutions (with the concentration of 0.01 to 2 M) shows the blocking effect of the polyaniline layer causing a significant decrease in transport characteristics in a wide range of concentrations of equilibrium solutions. A model of structural heterogeneity of composites is offered that takes into account the presence of an additional structural element, polyaniline, in the basic polymer matrix. Mechanisms of the observed barrier effects are discussed. Comparison of the transport-structural parameters of the MF-4SK membrane and MF-4SK/PAn composites allows elucidating the role of polyaniline in formation of transport routes for ion and solvent fluxes.     

Potentiometric monitoring DNA hybridization with polyaniline/Nylon-6 working electrode

Electrically conducting polymers are useful in various applications such as transistors and sensors. A potentiometric pH meter has been developed using polyaniline based working electrode and with improved selectivity using ionophores, the polyaniline based potentiometer has been applied to monitor various ions mainly in environmental applications. The polyaniline working electrode can be used to monitor not only the binding of a biological ionic macromolecules on polyaniline surface but also the binding of the adsorbed macromolecule with another macromolecule. We present first how the working electrode was prepared by polymerization of aniline in Nylon-6 matrix to provide the mechanical strength and then how single strand oligonucleotide probe binds with polyaniline surface. We then present how an electrode modification with mercaptoethanol results in a surface protected against non-specific binding and then finally we present the results of monitoring the complimentary strand binding leading to the formation of the double strand DNA. The text was submitted by the authors in English.     

Plasma polymerization of aniline on different surface functionalized substrates

The plasma polymerization of aniline on different surface functionlized low-density polyethylene (LDPE) substrates was investigated, and the resulting polymer was characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy. The results showed that the structure of plasma-polymerized polyaniline was rather different from polyaniline synthesized by conventional chemical and electrochemical methods. This difference may be due to extensive coupling reactions and cross-linking reactions during the plasma polymerization process. The use of acrylic acid graft copolymerized LDPE substrate significantly enhanced the adhesion of the polyaniline to the substrate over that observed with pristine LDPE. The plasma polymerized polyaniline can be rendered electrically conductive if the polymerization is carried out on a polystyrenesulfonic acid-coated LDPE substrate. Conductivity can also be induced by acid protonation of the polyaniline by HClO(4). The reaction of the plasma-polymerized polyaniline with viologen grafted on the substrate under UV irradiation and with AuCl(3) and Pd(NO(3))(2) in acid solutions was also investigated.     

Assessing the selectivity of composite ion-exchange membranes within the framework of the extended three-wire model of conduction

The possibility of assessing the selectivity of composite perfluorated membranes MF-4SK modified with polyaniline (PANI), based on the concentration dependence of their specific conductivity in terms of the extended three-wire model of conduction of ion-exchange materials is investigated. To check the reliability of results obtained, the transport numbers of ions are calculated based on the electrodiffusion coefficients of counter ions and coions determined from concentration dependences of conductivity and diffusion permeability of ion-exchange membranes. The transport numbers of hydrogen ions found by these two methods are shown to coincide with high accuracy throughout the whole range of concentrations of HCl solutions for the original MF-4SK membrane and membranes with the fixed thickness of the modified polyaniline layer on their one side. For the MF-4SK sample the with gradient distribution of polyaniline, which exhibits asymmetrical transport characteristics, the deviation between the transport numbers of ions calculated with the use of electrodiffusion coefficients of counter ions and coions and those determined in terms of the extended three-wire model of conduction is shown to increase with the increase in solution concentration but not exceed 4%.     

AFM morphological study of electropolymerised polyaniline films modified by surfactant and large anions

Atomic force microscopy (AFM) ex situ experiments were carried out in order to study morphologies of polyaniline films grown in the presence of an anionic surfactant, sodium dodecylsulphate (SDS), and also using different functionalised organic acids. Polyaniline film morphologies obtained in the presence of SDS were analysed in terms of the formation of a complex between the rodlike micelles and the anilinium cation in solution. For the different acids, the influence of anion size and the solubility of the oligomeric salt were considered to explain the different sizes of globular morphologies.     

Chemical trapping experiments support a cation-radical mechanism for the oxidative polymerization of aniline

The oxidative polymerization of aniline in aqueous acidic solution was carried out in the presence of a variety of organic compounds as potential traps for postulated intermediates. The polymerization was inhibited by hindered phenols and electron-rich alkenes, traps for cation-radicals. However, polyaniline was still obtained in the presence of electron-rich arenes, such as 1,3-dimethoxybenzene and 1,4-dimethoxybenzene, known as excellent receptors of nitrenium ions. Polymerization of N-phenyl-1,4-phenylenediamine was similarly carried out in the presence of potential traps. Polyaniline containing an N-phenyl group was obtained in the presence of 1,3-dimethoxybenzene and 1,4-dimethoxybenzene. Hindered phenols and 4-methoxystyrene only slightly inhibited polymerization of N-phenyl-1,4-phenylenediamine which most probably proceeded by way of the stable diarylamino radical. Copolymerization of aniline with 10 wt % of N-phenyl-1,4-phenylenediamine in the presence of these traps gave similar results to the polymerization of pure aniline. These results have led to the proposed cation-radical polymerization mechanism of aniline, in which the polymerization is a chain growth reaction through the combination of a polymeric cation-radical and an anilinium cation-radical. Step growth character is also present when a polymeric aminium cation-radical end combines with a diarylaminoended polymer. The copolymerization of N-phenyl-p-phenylenediamine can also occur by reaction of aniline cation-radical with a polyarylamine radical. The nitrenium mechanism was further rejected by the fact that attempted polymerization of N-phenylhydroxylamine, which forms authentic nitrenium ions in acid, failed to give polymer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2569–2579, 1999