Thermal stability of polypyrroles

The effect of dopants and level of doping on the thermal stability of polypyrrole at 90, 120 and 150°C in dry air and nitrogen was investigated by monitoring the decay of conductivity. Polymers doped with aromatic anions (p-toluene sulphonate and p-chlorobenzene sulphonate) exhibit better stability than polymers doped with an aliphatic anion (dodecyl sulphate). The conductivity decay appears to follow diffusion controlled kinetics. After an initial decrease in conductivity, polypyrrole doped with p-toluene sulphonate anion maintains a constant conductivity at 150°C in air for at least 4 weeks. Dedoping results in materials of lower conductivity but greater thermal stability. Differential scanning calorimetry (DSC) and thermogravimetry (TG) were found to be useful techniques to characterize and investigate thermal stability. Oxidation of polypyrrole films, monitored by DSC, shows diffusion controlled kinetics. Although both oxidation and conductivity decay show typical diffusion kinetics, oxidation is a necessary but not sufficient condition for the decay.     

Dopant-dependent variation in the distribution of polarons and bipolarons as charge-carriers in polypyrrole thin films synthesized by oxidative chemical polymerization

A study on the distribution of polarons vs. bipolarons as charge carriers in polypyrrole thin films doped with different dopant anions (chloride, p-toluenesulfonate and anthraquinone-2-sulfonate) is presented in this paper. The polypyrrole thin films synthesized by oxidative chemical polymerization have comparable thickness in the range of 80–100 nm. However, with the variation of the dopant anion, the conductivity of the polypyrrole thin films can differ by three orders of magnitude. The conductivity of polypyrrole thin films doped with chloride, p-toluenesulfonate and anthraquinone-2-sulfonate is 0.64 S/cm, 7.1 S/cm and 120 S/cm, respectively. The Raman spectroscopy and electron spin resonance (ESR) spectroscopy results show that (i) both polarons and bipolarons are present in the three types of polypyrrole thin films and (ii) the distribution of polarons vs. bipolarons as charge carriers in polypyrrole varies with the dopant anion used. The overall study reveals that the charge carriers in the anthraquinone-2-sulfonate-doped polypyrrole thin film are mainly spinless bipolarons, whereas the charge carriers in the chloride-doped polypyrrole thin film are dominated by paramagnetic polarons.     

Study of the factors determining the mobility of ions in the polypyrrole films doped with aromatic sulfonate anions

The electrochemical redox behavior of the polypyrrole (PPy) films doped with benzenesulfonate (BS), p-toluenesulfonate (pTS) and naphtalene-1,5-disulfonate (NDS) was investigated by cyclic voltammetry, the chemical composition of the films was determined by XDS, the surface morphology was characterized by AFM, and the interactions between pyrrole oligomers and the anions were modeled with quantum chemical methods. It is the first detailed comparative study of the properties of these interesting systems with two complementing interactions (electrostatic and aromatic stacking). It was shown than these relatively similar aromatic sulfonate anions have rather different behavior in PPy films. The results showed that the redoxactivity of polypyrrole films doped with sulfonate ions increases in the sequence pTS < BS < NDS. The comparison of voltammograms measured in the presence of different anions with PPy films synthesized in the same solution show that the PPy/pTS films have the most densely packed and the PPy/NDS films the least densely packed structure of the three. The mobility of ions in these films is mainly determined by the packing of the films, which in turn partly depends on the interactions between the dopant-anion and polymer chains.     

Fourier transform infrared study of polypyrrole–poly(vinyl alcohol) conducting polymer composite films: Evidence of film formation and characterization

The electrochemical preparation of polypyrrole (PPY)–poly(vinyl alcohol) (PVA) conducting polymer composite films on an indium–tin oxide glass electrode from an aqueous solution containing a pyrrole monomer, a p‐toluene sulfonate electrolyte, and a PVA insulating polymer is reported. The prepared PPY–PVA composite films were characterized by Fourier Transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and conductivity measurements. The FTIR study showed that the composite of PPY and PVA formed through bond formation between PVA and the p‐toluene sulfonate dopant anion. The conductivity data of PPY–PVA showed that with increasing PVA concentration in the pyrrole solution, the conductivity of the prepared PPY–PVA film increased up to a certain level due to an increase in conjugation length, and later, it decreased with further increases in the PVA concentration in the solution due to a decrease in conjugation length. This was supported by the FTIR band intensity I₁₅₆₀/I₁₄₈₀. The TGA results show that the PPY–PVA polymer composite film was thermally more stable than the PPY film. A shielding effectiveness of 45.6 dB was exhibited by the PPY–PVA composite film in the microwave frequency range. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4107–4113, 2006     

Current‐voltage characteristics of conducting polypyrrole in solid polyethylene oxide electrolytes

Current‐voltage characteristics were studied for polypyrrole films contacted with different electrolytes in aqueous form and complex polymer solid electrolytes. Cyclic voltammograms for the conducting polymer in aqueous medium exhibited the typical oxidation and reduction peaks, whereas for solid polymer electrolytes, there was large asymmetry in curves; with the anodic current being much higher than that in the cathodic region. A rapid switching‐type response was noted in the case of polyethylene oxide‐cupric chloride complex as solid electrolyte. This effect was pronounced when the same complex contained the polypyrrole deposited within it as a composite. These various results have been discussed in the light of different energy levels in the conducting polymer and the contacting medium, as well as the formation of a microdispersed system with higher charge transport. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2059–2067, 1999     

Exchange of counter anions in electropolymerized polyaniline films

Mobile counter anion exchange of electropolymerized polyaniline (PANI) films with the anions in acid solutions has been investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy, Raman, UV-vis, and fluorescence spectra. The studied acids include camphorsulfonic acid, p-toluene sulfonic acid, HCl, HClO₄, H₂SO₄ and H₃PO₄. In two cases of small and large counter ions of PANI films, CV tests have been performed alternately three times in each of two electrolytes containing organic or inorganic acid. The investigation of electrochemical and spectrophotometric measurements reveals that large counter anions can be easily replaced by the small anions; and the reverse exchange also occurs, but shows very low efficiency. This indicates that the achieved anion exchange in both cases leads to the remarkable alteration in electrochemical behavior and electrical conductance of PANI films. This implies counter anions, whatever the original or redoping ones, play an important role in the electrical, electrochemical, even optical properties of PANI. However, the polymer morphology does not be changed after exchange tests. This allows us to point out a ‘morphology-memory’ effect which is very significant for the development and application of PANI films with the same morphology and different properties.     

Preparation of poly(vinylidene fluoride)–polypyrrole composite films by electrochemical synthesis and their properties

Composite films of poly(vinylidenc fluoride–polypyrrole (PVDF–PPy) were prepared by electrochemical polymerization of pyrrole on a very thin PVDF matrix film (～ 0.5 μm). The polymerization was carried out in aqueous media using stainless steel, coated with PVDF matrix, as a working electrode, and p-toluene sulfonate (PTS), as a dopant. The films were prepared at different voltages for different durations of time in order to optimize the conditions of composite formation. The resulting films were characterized by studying IR spectra, conductivity, SEM, XRD, and tensile strength measurements. The mechanical properties of the composites were found to have improved, while the conductivity remained more or less same as that of pure PPy. © 1995 John Wiley & Sons, Inc.     

Importance of poly(ethylene oxide)-modification and chloride anion for the electron transfer reaction of cytochrome c in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide

Horse heart cytochrome c (cyt c) was chemically modified with poly(ethylene oxide) (PEO) to dissolve it in room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([emim][TFSI]). The redox response of the modified cyt c, hereafter PEO-cyt c, was analyzed in [emim][TFSI]. PEO modification to the surface of cyt c, which exceeded 60% of the total mass of the PEO-cyt c, was an effective method to solubilize the cyt c. In spite of the high ion density and sufficient ionic conductivity of [emim][TFSI], no redox response of pure PEO-cyt c was detected. However, a reversible redox response of PEO-cyt c was observed after adding a simple electrolyte such as KCl to [emim][TFSI]. The redox response of PEO-cyt c was sensitive to the anion radius of the added salt, and the chloride anion was found to be the best anion species to produce a redox response of PEO-cyt c in [emim][TFSI]. However, above a certain salt concentration, the resulting increase in solution viscosity would suppress the redox reaction. The results strongly indicate that the chloride anions, because of their mobility in the polypeptide matrix, compensate the charge change of heme during the electron transfer reaction. Larger anions did not show such an effect due to sterical restrictions on the migration through the protein shell to the heme pocket of cyt c.     

On the morphology and growth of electrochemically polymerized polypyrrole

Samples of polypyrrole p-toluene sulfonate have been prepared by electrochemical polymerization from aqueous and methanolic solutions. The morphology and molecular ordering have been studied by scanning and transmission electron microscopy, polarizing optical microscopy and wide-angle X-ray scattering. Specimens prepared from aqueous solution develop as compact films, which exhibit considerable molecular anisotrophy; cross-sections are highly birefringent and the local molecular orientation is found to correlate with the nodular surface features. Transmission electron microscopy also reveals evidence of supermolecular ordering within the films, which is consistent with the optical observations. Samples prepared from methanolic solutions appear very different: no evidence of molecular anisotropy or internal subdivision has been observed. These films are massively voided as a result of extensive internal delamination, which occurs after the polypyrrole is deposited onto the work electrode. On the basis of the observed morphologies, modes of growth are proposed, based upon polymerization in solution followed by a degree of further chain development after precipitation.     

Cellulose in lithium chloride/N,N-dimethylacetamide, optimisation of a dissolution method using paper substrates and stability of the solutions

Activation and dissolution in lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) of cellulose from paper substrates are studied. The importance of the multiple parameters involved such as salt concentration, sample source and preparation is shown in a literature review. The experiments are carried out in order to perfect the method of activation and dissolution of paper containing different kinds of additives, typically found in historic papers. The suitability and efficiency obtained in the different trials are evaluated. The final procedure involves the activation by solvent exchange, with a water/methanol/DMAc sequence, followed by dissolution in 8% LiCl/DMAc at 4 °C. A study of the stability of the cellulose solutions in the experimental conditions showed that no degradation nor aggregation occurred during the solvation process and even after several months and confirmed the non-aggressiveness of LiCl/DMAc.     

Poly(N-methylpyrrole) electrodeposited on copper: Corrosion protection properties

Electrochemical synthesis of poly(N-methylpyrrole) films on copper electrodes from an aqueous oxalic acid has been achieved. A potential higher than 2 V (SCE) was needed to generate the polymer, for this reason, the polymer was in the overoxidized state. The inhibiting corrosion properties of this coating on copper were investigated for the first time in aqueous 0.1 M sodium chloride solution using potentiodynamic polarization, Tafel analyses, open-circuit potential and electrochemical impedance spectroscopy. Corrosion protection properties comparable to those of polypyrrole (PPy) films were observed for these films. A physical barrier effect is the most likely protection mechanism.     

A novel codoping approach for enhancing the performance of polypyrrole cathode in a bioelectric battery

A conducting polymer (CP) based bioelectric battery provides a promising alternative to commercial lithium batteries to drive biomedical devices. However, the low power density limits practical application. Here, we synthesize a polypyrrole (PPy)/anthraquinone sulfonate (AQS)/reduced graphene oxide (r-GO) composite via a facile electrochemical route, and use this as a novel cathode material for bioelectric batteries. The presence of r-GO significantly enhanced the electrochemical properties of PPy and led to greatly improved cell performance compared to that of PPy/AQS. The resultant PPy/AQS/r-GO composite delivered a maximum power density of 6240.5 mW m⁻², 14.2 times higher than that of PPy/p-toluenesulfonate (pTS) as reported previously.     

Synthesis, characterization and thermal properties of soluble aromatic poly(amide imide)s

Novel diamines such as N,N′-bis(aminoaryl)terephthalamido-2-carboxylic acids (BATCA), which contain primary amine, amide and carboxylic acid groups and are soluble in dilute aqueous NaOH solution, were synthesized by reacting aromatic diamines with trimellitic anhydride chloride in dimethylformamide. Poly(amide imide)s containing 3:1 ratio of amide:imide groups in the polymer chain were prepared by low temperature solution polymerization of BATCAs with isophthaloyl chloride or terephthaloyl chloride in dimethylformamide at 5-10 °C to form poly(amide amic acid)s, and followed by treating with a mixture of triethylamine and acetic anhydride. The PAIs were soluble in polar aprotic solvents like dimethylformamide, dimethylacetamide, dimethylsulphoxide and N-methylpyrrolidone, and have inherent viscosities in the range of 0.30-0.66 dL/g. The PAIs were characterized by IR, ¹H NMR and ¹³C NMR techniques. Thermogravimetric analysis (TGA) has shown that the initial decomposition temperatures of the polymers are in the range of 250-440 °C, depending upon the structures of diamine and diacid chloride. The glass transition temperatures of the PAIs are in the range of 128-320 °C. The IDT and T_g values of the polymers containing terephthaloyl unit are higher by about 20-40 °C than those of the polymers with isophthaloyl unit. BATCA could be utilized for the preparation of thin film composite membranes having PAA/PAI barrier layer on PES by in situ interfacial polymerization with IPC/TPC/TMC.     

Effects of applied potentials on permselectivity of ions through polypyrrole/porous-polypropylene composite membrane

A composite membrane was prepared by the combination of polypyrrole with a porous-polypropylene film, and its permselectivity was investigated. The permeability and selectivity of various sodium salts through the membrane were changed with an applied potential. The permeation of anions at the positive potentials was due to the migration through the positive sites of the polypyrrole layer, as well as the diffusion from the difference of concentration and potential. The contribution of the migration effect to the anion permeation was very large. The main factors dominating the permeation character of different anion species were the size and valence of the anions. The composite membrane worked effectively as a functional separation membrane to control the ionic permeability by potential application. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 647–653, 1998     

Morphological characterization of γ-LiAlO2-filled composite polymer electrolytes containing LiPF6

Morphological properties of composite polymer electrolytes based on blends of polyethylene oxide (PEO) and a perfluorinated polyphosphazene (PPz) containing LiPF₆ as lithium salt and a finely divided ceramic filler, γ-LiAlO₂, were studied by using polarizing optical microscopy and differential scanning calorimetry (DSC). A parallel study was performed on propylene carbonate plasticized composite polymer electrolytes. Results indicate that both the morphology and the thermal properties depend upon the composition of the polymer host, a result not observed in composite polymer electrolytes having the same polymer composition containing LiCF₃SO₃ as lithium salt. The incorporation of the ceramic filler at the lower concentration tested (10% by wt) has practically no effect on the thermal behavior of the samples; whereas, differences were clearly distinguished at a concentration of ceramic material of 20 wt %. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1023–1030, 1999     

A study on the electro-oxidation and electropolymerization of a new OPE linear molecule by EQCM and in situ FTIR spectroelectrochemistry

A novel symmetric conjugated oligo(phenylene-ethynylene) (OPE) linear molecule (1,4-bis(4-aminophenylethynyl)benzene); BAB) was synthesized by Sonogashira cross-coupling reactions. The structure and purity of the compound were confirmed by ¹H NMR, ¹³C NMR and infrared (IR) and mass spectrometry (MS). The electrochemical oxidation process and mechanism of BAB were investigated via in situ Fourier transform infrared (FTIR) spectroelectrochemistry and electrochemical quartz crystal microbalance (EQCM). The electrochemical oxidation mechanism of BAB was proposed. The studies revealed that the BAB concentration and oxidation potential had a significant influence on the growth of the polymer film. A densely packed polymer film, which exhibited nonelectroactivity, was formed when a high monomer concentration and a high oxidation potential were used. When the electropolymerization of BAB was conducted at a lower concentration, a new pair of redox peaks appeared, and the resultant thin film had better electroactivity. The in situ FTIR studies confirmed that BAB could be electro-oxidized into radical cations and then electropolymerized via para (N-N) and/or ortho (N-C) coupling reactions to form polymers with a larger conjugated π-electron system. The surface morphology of the poly-BAB was also investigated with atomic force microscopy (AFM) and scanning electron microscopy (SEM).     

Extraction of mercury and silver into base-acid treated polypyrrole films: A possible pollution control technology

Polypyrrole-para-toluene sulfonate films were treated sequentially in 0.5 M NaOH and 0.5 M HNO₃. The base treatment was reported to deprotonate the film, resulting in the removal of the p-toluene sulfonate counter ions. On the other hand, the acid treatment was found to result in reprotonation of the film and its return to an oxidised state. In this work, such a treatment of polypyrrole films was initially exploited in an electroless entrapment of mercury from standard solutions. An electrochemical stripping technique was used to remove the entrapped mercury from the film. A linear relationship between the amount of mercury electrolessly entrapped within the film and that being stripped off from the films was obtained (correlation coefficients range from 0.992 to 0.997, N = 4). Several characteristics of these mercury-loaded polypyrrole films including the morphology, point of saturation and the effect of interfering silver ions were then investigated. The capability of base-acid pretreated polypyrrole films to remove mercury by electroless preconcentration in mercury-containing wastewater samples was then demonstrated. The mercury contents determined in these samples are comparable to those obtained using inductively coupled plasma-atomic emission spectroscopy. Furthermore, using silver as an example, we were able to achieve electroless preconcentration of the metal into pretreated polypyrrole films following a time as short as 7 min. All these results tend to suggest that the base-acid pretreated polypyrrole films may find an application as a simple, cheap and effective pollution control technology.     

Ruthenium based DSA® in chlorate electrolysis—critical anode potential and reaction kinetics

Ruthenium based DSA®s have been investigated in chlorate electrolyte using rotating discs made from commercial electrodes. Measurements of the voltammetric charge, q*, and of iR-corrected polarisation curves up to current densities of 40 kA/m² were recorded on new anodes and on aged anodes from 3 years of production in a chlorate plant. Anodic polarisation curves in chloride containing electrolytes bend towards a higher slope at approximately 1.2 V versus Ag/AgCl, likely due to oxidation of ruthenium. The potential and current density at which the curves bend have been defined as the critical potential, E_cr, and the critical current density, i_cr. New anodes that operate at a relatively high potential, >E_cr, obtain an increase in real surface area and thereby a decrease in anode potential and in the selectivity for oxygen formation during the first months of operation. Experiments at constant ionic strength under chlorate process conditions showed that E_cr decreased with increasing chloride concentration with a factor of −0.09 V/log Cl⁻, whereas i_cr increased with increasing chloride concentration. The chlorine evolution reaction was of the first order with respect to chloride concentration. A possible reaction mechanism for chlorine formation is suggested.     

Lithium-polymer battery based on an ionic liquid-polymer electrolyte composite for room temperature applications

A lithium-polymer battery based on an ionic liquid-polymer electrolyte (IL-PE) composite membrane operating at room temperature is described. Utilizing a polypyrrole coated LiV₃O₈ cathode material, the cell delivers >200 mAh g⁻¹ with respect to the mass of the cathode material. Discharge capacity is slightly higher than those observed for this cathode material in standard aprotic electrolytes; it is thought that this is the result of a lower solubility of the LiV₃O₈ material in the IL-PE composite membrane.     

Preparation and electrochemical properties of polyaniline doped with benzenesulfonic functionalized multi-walled carbon nanotubes

Nanocomposite of benzenesulfonic functionalized multi-walled carbon nanotubes doped polyaniline (PANi/f-MWCNTs) was synthesized via a low-temperature in situ polymerization method. The PANi/f-MWCNTs composite has a thin film of PANi coating uniformly on the surface of the f-MWCNTs. The electrochemical results show that PANi/f-MWCNTs nanocomposite possesses good rate response, which could ascribe to the uniform structure and the better conductivity of composite as well as the in situ doping/de-doping process between the benzenesulfonic acid groups of f-MWCNTs and PANi chain. In addition, the composite also has better capacity and cyclability than PANi/p-MWCNTs composite. It could attribute to the presence of f-MWCNTs, which makes more electrolyte contact with PANi to participate in faradaic redox reactions and dopes with the PANi polymer chain through the benzenesulfonic acid groups to form stable polyemeraldine salts.