A correlation of electrochemical and spectroelectrochemical properties of poly(o-toluidine)

A comparative discussion of the electrochemical and spectroelectrochemical properties of poly(o-toluidine) POT, a methyl substituted derivative of polyaniline, PANI, is presented. POT exists in various oxidation states and shows an insulator to conductor transition when doped by electrooxidation. The transformation of the polymer film from its non-conducting leucoemeraldine to its conducting emeraldine state and further on to its again non-conducting pernigraniline form was observed with different techniques including cyclic voltammetry, in situ conductivity measurements and in situ UV-vis and Raman spectroelectrochemical methods. Results reveal that POT shows a good correlation between its electrochemical and spectroelectrochemical properties in its different oxidation states.     

Spectroscopic study of polytoluidines in the UV-visible and IR regions

Electropolymerization of o-toluidine(o-methylaniline) and m-toluidine was carried out in acidic aqueous solution, and UV-visible and IR spectra of the resulting polymer films were obtained at various electric potentials and pHs. In Na₂SO₄ aqueous solution, poly(o-toluidine) gave considerably different UV-visible spectra from polyaniline, whereas, in HCl (pH ～ 0), the spectra of poly(o-toluidine) changed in the same way as polyaniline when the potential was varied. This spectral change depended also on counterion. This suggests that the intermediate state (radical cation) of poly(o-toluidine) is unstable in a neutral solution especially when a large counter ion exists, which is contrast to polyaniline. The dependency of the FT-IR spectra of poly(o-toluidine) on the potential and pH supported also the above result of UV-visible spectra. From both UV-visible and IR spectra under various conditions, it was found that o-toluidine and m-toluidine give the same polymer.     

Preparation and characterization of fully oxidized form of polyaniline

Summary The oxidation state of polyaniline (PANI) can be varied from the fully reduced leucoemeraldine base (LEB) to the half oxidized emeraldine base (EB) and to the fully oxidized form pernigraniline base (PNB). In this work, the synthesis and properties of the highest oxidation state of polyaniline, pernigraniline, in the base as well as the corresponding salt form are discussed. Received: 10 May 2000/Revised version: 1 August 2000/Accepted: 1 August 2000     

Thin film polyaniline-polyaniline electrochemical cells

Electrodeposited polyaniline (PANT) in the emeraldine oxidation state was used as the electrodes of open rechargeable cells containing 1 m HClO₄ as the electrolyte. The cells could be charged at very high hourly rates to 85% of the redox charge in the leucoemeraldine-emeraldine transition of the polymer. Contrary to normal behaviour of rechargeable cells, the coulombic efficiency improved with increasing rates of charge injection and withdrawal. This is attributed to less charge being dissipated by self-discharge at high rates of discharge. The poor charge retention was caused by reactions between the charged electrodes and their environment. The decrease in cell voltage on standing may also be induced by internal redox reactions of PANT of different oxidation states present at the electrodes as a result of incomplete oxidation or reduction during cell operation. Ultraviolet (u.v.) spectroscopy of the charged electrodes identified mostly protonated leucoemeraldine at the negative electrode and pernigraniline at the positive electrode. The irreversibility in the oxidation from the emeraldine state to the pernigraniline state accounts mostly for the degeneration of cell performance after prolonged cycling.     

Comparison between different conditions of the chemical polymerization of polyaniline on top of PET films

Composites produced during the in situ chemical polymerization of aniline on top of a poly(ethylene terephthalate) (PET) film, in different conditions, were studied by open‐circuit potential (Voc), ultraviolet‐visible, and infrared spectroscopy, electrical conductivity measurements, scanning electron microscopy, and atomic force microscopy. The polymerization monitoring by Voc showed a maximum associated with the intermediate pernigraniline oxidation state and a final formation of polyaniline (PANI) in the doped emeraldine salt (ES) form. Furthermore, high electrical conductivity values were obtained for the PANI–ES coating prepared under selected conditions. A globular formation was observed for the doped PANI–ES coating with globules of sizes of the same order and same shape of the PET, demonstrating the influence of the substrate on the coating morphology. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1220–1229, 2001     

Inexpensive Fabrication and Characterization of Crystalline Poly(o-Anthranilic Acid-co-o-Phenylenediamine) Emeraldine Base/Bentonite Nanocomposites

Copolymers of o-anthranilic acid and o-phenylenediamine/hydrophilic bentonite nanocomposites were synthesized by 1:1 molar ratios of the respective monomers with different percentages of nanoclay through modified in situ chemical copolymerization. The results obtained were justified by measuring the Fourier transform infrared of poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base/bentonite nanocomposites. Ultraviolet–visible spectra of poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base/bentonite nanocomposites were investigated. The thermal stability was studied, and it was found that poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base/bentonite nanocomposites were thermally more stable than pure copolymer. X-ray diffraction patterns of copolymer poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base and poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base/bentonite nanocomposites were studied.     

On the molecular properties of polyaniline: A comprehensive theoretical study

A comprehensive study about the molecular and electronic properties of the different forms of polyaniline has been developed using quantum mechanical calculations. Initially the performance of different ab initio and DFT quantum mechanical methods has been evaluated by comparing the results provided for small model compounds containing two repeating units. After this, calculations on the emeraldine base, leucoemeraldine base, pernigraniline base and emeraldine salt (monocationic and dicationic) forms of oligoanilines with n repeating units, where n ranged from 5 to 13, have been performed using the BH&H/6-31G(d) method, which was found to be a very suitable theoretical procedure. Interestingly, calculations indicate that the distribution in blocks of the repeating units containing amine and imine nitrogen is largely preferred for the emeraldine base form. On the other hand, the molecular structure and band gap of the emeraldine base, leucoemeraldine base and pernigraniline base forms have been rationalized according to their differences in the conjugation of the C₆H₄ rings. Calculations on cationic oligoanilines indicate that, when the emeraldine salt form presents a doublet electronic state, the positive charge and the spin density are located in the middle of the chain extending through five consecutive repeating units.     

Comparative studies of electrochemically deposited poly(o-toluidine) and poly(m-toluidine) films

Under galvanostatic deposition conditions poly(o-toluidine) exhibits a higher rate of polymerization than poly(m-toluidine). This observation is supported by results obtained by different characterization techniques such as spectrophotometry, scanning electron microscopy and thermogravimetric analysis. The monomer concentration was found to be the predominant parameter in obtaining selectively a conducting salt phase in both cases. However, the morphology of these polymeric films does not reveal any particular relationship with monomer concentration; instead a mixed morphology, i.e. a combination of granules and fibres, is observed. Finally, the thermal stability of poly(m-toluidine) is lower than that of poly(o-toluidine) with a shift of 190°C in the final decomposition temperature.     

Corrosion performance of chemically synthesized poly(aniline-co-o-toluidine) copolymer coating on mild steel

A soluble copolymer from aniline and o-toluidine [poly(aniline-co-o-toluidine)] was synthesized by chemical oxidative copolymerization using ammonium persulphate as an oxidant in hydrochloride aqueous medium. The resultant copolymer was characterized by Fourier Transform Infrared (FTIR) spectroscopy and chemically deposited on mild steel specimens using N-methyl-2-pyrrolidone (NMP) as solvent via solution evaporation method. The anticorrosive properties of copolymer coating was investigated in major corrosive environments, such as 0.1 M HCl, 5% NaCl solution, artificial seawater, distilled water and open atmosphere by conducting various corrosion tests which include: immersion test, open circuit potential (OCP) measurements, potentiodynamic polarization measurements and atmospheric exposure test. The corrosion performance of copolymer coating was also compared separately with polyaniline (PANi) and poly(o-toluidine) (POT) homopolymer coatings. The surface morphologies of polymer coatings were evaluated using scanning electron microscopy (SEM). The synthesized copolymer exhibited excellent protection against mild steel corrosion; the protection efficiency being in the range of 78–94% after 30 days of immersion. The corrosion performance of copolymer in 5% NaCl and artificial seawater was comparable, which was only marginally better than in 0.1 M HCl. In general, the performance of copolymer coating was found to be better than that of homopolymer coatings.     

Preparation and electrochemical behavior of dopamine-selective polymeric membrane

Summary o-toluidine was polymerized electrochemically using constant-potential electrolysis at a gold electrode surface. Electrochemical behavior of dopamine and ascorbic acid at the polymer electrode prepared in this manner was examined by cyclic and differential pulse voltammetry techniques. The influence of chemical and electrochemical variables on dopamine selectivity of the polymer electrode was systematically investigated and the optimal values for each parameter were determined. Experimental results showed that optimized polymeric membrane exhibited selectivity for dopamine while blocking ascorbic acid. Therefore, it is claimed that poly (o-toluidine) film can be used as a dopamine-selective polymeric membrane in the presence of ascorbic acid. Key Words: poly (o-toluidine); selective membrane; dopamine Received: 22 November 1999/Revised version: 25 January 2000/Accepted: 10 February 2000     

Electroactive polymer films for stainless steel corrosion protection

Electroactive polymer films of polyaniline, poly-o-toluidine and a composite of both were deposited on stainless steel and their performance as protective coatings against corrosion was evaluated. Open circuit potential and potentiodynamic studies of the polymer-coated stainless steel in a corrosive medium showed a significant shift in the corrosion potential towards more positive values. Mechanical characteristics of the films were evaluated by means of microhardness measurements, revealing nonelastic films in all cases and low hardness values that increased from polyaniline to poly-o-toluidine to the composite. The best results were obtained in the case of the polyaniline-o-toluidine composite.     

Copolymers of aniline and o‐methoxyaniline. II. Thermoanalytical studies

A study on the thermal stability, thermodynamical parameters, especially relaxation transition temperature (T_g), and their change upon irreversible reactions (crosslinking, postpolymerization, decomposition, etc.) taking place on heating of the undoped homo‐ and copolymers of aniline and o‐methoxyaniline was performed by using differential scanning calorimetry. It was found that polyaniline and its oligomers might be responsible for the postpolymerization process observed on heating thermograms of the polymers in their emeraldine base form. It can be stated that the proceeding of this process appears to be a reason for the higher thermal stability of polyaniline when compared with poly(o‐methoxyaniline). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2729–2734, 2007     

Local pH-controlled reactivity investigations by thin-layer scanning tunnelling microscopy

A newly designed thin-layer STM (TLSTM) technique is presented based on a microfabricated probe combining an electrolytic STM probe with an annular iridium oxide microelectrode operating as a potential-controlled generator or scavenger of H⁺. This TLSTM configuration can be used to combine in situ STM studies of electrode processes with the simultaneous investigation of H⁺ flux integrals associated with the electrode reaction. In this paper, the technique is applied to investigate the H⁺ exchange behaviour of electropolymerised polyaniline films and associated STM-relevant properties in 0.5 M NaClO₄+10⁻² M HClO₄. For a polyaniline film kept in the intermediate (emeraldine) oxidation state at 0 mV versus MSE it is shown that its thickness increases due to H⁺ insertion if the pH is lowered from pH 2 to ca. 1.6, and that its conductivity decreases significantly if the pH is increased from 2 to ca. 12. In a second experiment, where the exchange of H⁺ at pH 2 is monitored during film oxidation and reduction within the potential range of both redox transfer steps, it is shown that significant exchange of H⁺ occurs only in the interval of the second (emeraldine/pernigraniline) redox transfer.     

Study on soluble polyaniline by positron annihilation technique

The solubility, electrical conductivity, and other properties of polyaniline (PANI) are highly dependent on its oxidation state. In this work, polyaniline (PANI1) prepared by peroxodisulphate induced polymerization of aniline in acidic aqueous medium in presence of benzenediazonium chloride salt was found to exist in lower oxidation state than emeraldine form of PANI and was highly soluble in common organic solvents. This polymer was subjected to positron annihilation spectroscopic study to investigate the correlation between the oxidation state of the polymer and defect sites generated by different degrees of protonation that in turn affect its electrical conductivity. The positron annihilation lifetime data were resolved to yield a three‐component fit for PANI1 subjected to different levels of protonation. The variation of positron annihilation parameters (τ_1,I₂) and Doppler broadening parameters (R, S) as a function of protonation level of the polymer indicate the dopant sites increase initially on protonation and reach a saturation value after a certain level of acidification. The lower value of electrical conductivity and the intensity of intermediate lifetime component (I₂) for PANI1 compared to PANI in emeraldine oxidation state indicate the presence of lesser number of quinoid–imine moieties that could undergo protonation and thus yield highly enriched trapping centers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of poly(o‐toluidine) doped with organic sulfonic acid by solid‐state polymerization

Poly (o‐toluidine) (POT) salts doped with organic sulfonic acids (β‐naphthalene sulfonic acid, camphor sulfonic acid, and p‐toluene sulfonic acid) were directly synthesized by using a new solid‐state polymerization method. The FTIR spectra, ultraviolet visibility (UV–vis) absorption spectra, and X‐ray diffraction patterns were used to characterize the molecular structures of the POT salts. Voltammetric study was done to investigate the electrochemical behaviors of all these POT salts. The FTIR and UV–vis absorption spectra revealed that the POT salts were composed of mixed oxidation state phases. All POT salts contained the conducting emeraldine salt (half‐oxidized and protonated form) phase; the pernigraniline (fully oxidized form) phase is predominant in POT doped with β‐naphthalene sulfonic acid, and POT doped with p‐toluene sulfonic acid had the highest doping level. The X‐ray diffraction patterns showed that the obtained POT doped with organic sulfonic acids were lower at crystallinity. The conductivity of the POT salts were found to be of the order 10^?3‐10^?4 S/cm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1630–1634, 2005     

Self-Assembly of Methyl Substituted Polyaniline Hollow Nanospheres in a Polyelectrolyte Solution

Hollow nanospheres of poly(m-toluidine), poly(o-toluidine), and poly(N-methylaniline) were successfully prepared in a solution of poly(methyl vinyl ether-alt-maleic acid) by using ammonium persulfate as the oxidant. The polymerization processes of methyl substituted aniline were monitored by recording pH and temperature changes of the reaction medium. The experimental results showed that the substitution position of methyl group affected the characteristics of formed hollow nanospheres. The formation mechanism of such hollow nanospheres was suggested. The produced hydrophobic oligomers self-assembled at the interface of water/droplet of monomers and acted as the soft template for the formation of hollow spheres.     

Corrosion protection aspects of electrochemically synthesized poly(o-anisidine-co-o-toluidine) coatings on copper

The poly(o-anisidine-co-o-toluidine) coatings were synthesized on copper substrates by electrochemical copolymerization of o-anisidine with o-toluidine using sodium salicylate as supporting electrolyte. These coatings were characterized by cyclic voltammetry, UV-vis absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and scanning electron microscopy (SEM). The formation of the copolymer with the mixture of monomers in the aqueous sodium salicylate solution was ascertained by a critical comparison of the results obtained with the polymerization of the individual monomers, o-anisidine and o-toluidine, respectively. The corrosion protection aspects of poly(o-anisidine-co-o-toluidine) coatings to copper was investigated in aqueous 3% NaCl solution by potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results of the potentiodynamic polarization measurements and EIS studies showed that the poly(o-anisidine-co-o-toluidine) coatings provided the effective corrosion protection to copper than that of respective homopolymers. The corrosion rate is observed to depend on the feed ratio of o-toluidine used for the synthesis of the copolymer coatings.     

The reaction of polyaniline with iodine

Polyaniline (PANI) (emeraldine) base has been exposed to iodine in an ethanol-water suspension. The conductivity of PANI increased from 10⁻⁹ S cm⁻¹ to 10⁻⁴ S cm⁻¹ already at the molar ratio [I₂]/[PANI] = 1, and a higher content of iodine had only a marginal effect. This is the result of the protonation of PANI base with hydriodic acid, which is a by-product of the oxidation of the emeraldine form of PANI to pernigraniline constitutional units. The reaction is discussed on the basis of FTIR spectra. An alternative reaction, a ring-iodination of PANI, is marginal. Only one iodine atom substitutes a hydrogen atom in about 12 aniline units, even at high iodine concentration, [I₂]/[PANI] = 8. The film of polyaniline base can be used in sensing iodine; after exposure to the iodine vapor, the conductivity of the polyaniline film increased.     

Synthesis and characterization of conducting copolymers from aniline and o‐anisidine in HCl solutions

Conducting poly(aniline‐co‐o‐anisidine) (PAS) films with different ratios of aniline units in the polymer chain were prepared by oxidative polymerization of different molar ratios of aniline and o‐anisidine in 1 M HCl using cyclic voltammetry. Due to the much higher reactivity of o‐anisidine, the structure and properties of PASs were found to be dominated by the o‐anisidine units. The polymerization of poly‐o‐anisidine and PASs followed zero‐order kinetics with respect to formation of the polymer (film thickness) and the autocatalytic polymerization of aniline was completely inhibited. In contrast to polyaniline, a decrease in the polymerization temperature was found to increase the amount of copolymer formed and its redox charge. The presence of aniline units in PASs led to a pronounced increase in the molecular weight and conductivity, and a decrease in the solubility in organic solvents. Repetitive charging/discharging cycles showed that PASs resist degradation more than polyaniline. Copyright © 2003 Society of Chemical Industry     

Electrochemical and in situ TM-AFM studies of the polymerization conditions on poly(o-methoxyaniline) film morphology

The in situ atomic force microscopy and the electrochemical studies on electropolymerization of the o-methoxyaniline in the 0.0-0.8 V versus NHE range of the electrode potential are described. It is proved that in the 0.0-0.3 V versus NHE a redox process takes place, resulting in the formation of poly(o-methoxyaniline) in its reduced form, leucoemeraldine. The different morphologies are exhibited by poly(o-methoxyaniline) under different polymerization conditions. The microscopic results show that with the increase of the monomer concentration in the bulk of electrolyte solution the globular morphology, related to the coil like molecular structure, is replaced by the fibrilar one, related to the opened-up, more conductive extended coil structure. It is shown that oxidation of a leucoemeraldine state of polymer to its emeraldine state results in the change of the morphology from the chain like structure to the massive fibrilar like structure. The reduction of oxidized polymer results in its irreversible fragmentation.