New method of synthesis of electroactive polyamide with amine‐capped aniline pentamer in the main chain

A novel way to prepare an electroactive polyamide (alternating copolymer) is presented. Well‐defined molecular structure polyamide with amine‐capped aniline pentamer in the main chain was obtained. The copolymer has been characterized by Fourier‐transform infrared (FTIR) spectra, ¹H NMR, elemental analysis (EA), and gel permeation chromatography (GPC). Its chemical oxidation process was studied by UV–vis spectra and the electrochemical analysis was checked by cyclic voltammetry (CV). It was found that the obtained electroactive polyamide shows three redox peaks in the cyclic voltammetry, which is different from the polyaniline. Moreover, the thermal properties of the copolymer were evaluated by thermogravimetric analysis (TGA). The electrical conductivity is about 2.5 × 10^?6 S cm^?1 at room temperature. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 477–482, 2006     

Water‐resistant conducting hybrids from electrostatic interactions

Conductive hybrids were prepared in a water/ethanol solution via the sol–gel process from an inorganic sol containing carboxyl groups and water‐borne conductive polyaniline (cPANI). The inorganic sol was prepared by the hydrolysis and condensation of methyltriethoxysilane with the condensed product of maleic anhydride and aminopropyltriethoxysilane as a catalyst, for which the carboxyl counterion along the cPANI backbone acted as an electrostatic‐interaction moiety. The existence of this electrostatic interaction could improve the compatibility of the two components and contribute to the homogeneous dispersion of cPANI in the silica phase. The electrostatic‐interaction hybrids displayed a conductivity percolation threshold as low as 1.1 wt % polyaniline in an emeraldine base, showing 2 orders of magnitude higher electrical conductivity than that without electrostatic interactions. The electrostatic‐interaction hybrids also showed good water resistance; the electrical conductivity with a cPANI loading of 16 wt % underwent a slight change after 14 days of soaking in water. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1424–1431, 2007     

Facile synthesis and characterization of the copolymers and their pure nanoparticles from aniline with 4‐sulfonic diphenylamine

Copolymer nanoparticles from aniline (AN) and 4‐sulfonic diphenylamine (SDP) were simply synthesized for the first time by an oxidative precipitation polymerization with inorganic oxidants in an acidic aqueous medium without any external emulsifier or stabilizer. The polymerization yield, intrinsic viscosity, solubility, solvatochromism, electrical conductivity, and thermal stability of the copolymers were systematically studied through changes in the AN/SDP ratio, polymerization temperature, oxidant species, monomer/oxidant ratio, and acidic medium. The molecular structure of the copolymers was characterized with elemental analysis, IR, and ultraviolet–visible spectra. The polymers exhibited very good solubility in polar solvents, water, and NH₄OH, and this was mainly attributable to the presence of sulfonic acid side groups. The electrical conductivity of the copolymers increased greatly, from 6.00 × 10^?4 to 2.55 × 10^?1 S/cm, with increasing AN content. The size of the copolymer particles, determined by laser particle analysis and atomic force microscopy (AFM), strongly depended on the polymer state and oxidant/monomer ratio. Pure dedoped particles of the AN/SDP (50/50) copolymer at an oxidant/monomer ratio of 1/2 exhibited minimum length/diameter ratios of 62/44 and 45/30 nm by AFM and transmission electron microscopy, respectively. The copolymers showed typical four‐step weight‐loss behavior in nitrogen and air and higher thermostability in nitrogen. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3380–3394, 2004     

Corrosion studies of polyaniline/coconut oil poly(esteramide urethane) coatings

Advancements in the area of conducting polymers have been towards their application as effective corrosion protective coatings to replace the use of heavy metals as additives in the coatings industries, which are now considered to be an environmental as well as health hazard. With the aim to utilize a sustainable resource based polymer for the development of an anti‐corrosive conducting coating material, coconut oil based conducting blend coatings of polyaniline and poly(esteramide urethane) were prepared by loading different ratios (2, 4 and 8 wt%) of polyaniline in poly(esteramide urethane). Then their physico‐chemical, thermal, morphological, conductivity and anti‐corrosive coating characteristics were investigated. The effect of a 2 year environmental aging process on the coated samples was analyzed by thermal methods as well as by corrosion studies. Results showed that the corrosion protective performance of the blend coatings was far superior than that of plane poly(esteramide urethane). These coatings showed enhanced corrosion protection in acid as well as alkaline environments upto 360 and 192 hr respectively. Conductivity of the blends was found to be in the range 2.5 × 10^?5–5.7 × 10^?4 S/cm^?1. An increase in the thermal stability of the blend coatings and a decrease in their conductivity was noticed in the aged samples which was attributed to the crosslinking effect. The corrosion protective performance of the coatings remained almost unaffected even after 2 years of aging. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and characterization of polyaniline nanoparticles in phosphonic acid amphiphile aqueous micellar solutions for waterborne corrosion protection coatings

Polyaniline (PANI) dispersions consisting of 270 to 380 nm sized particles were prepared by oxidation with ammonium peroxydisulfate (APS) in n‐decylphosphonic acid (DPA) micellar solutions. The green dispersions do not undergo macroscopic precipitation for more than a year. The synthesized DPA doped PANI exhibited enhanced electrical conductivity (3.6 S cm^?1 ) compared with DPA‐PANI (2.3 x 10 ^{? 4} S cm ^{? 1}) prepared by postsynthesis treatment of the PANI‐base with DPA. It was shown that through protonation with decylphosphonic acid, polyaniline showed a significantly enhanced solubility in common organic solvents like chloroform, xylene, etc. The synthesized PANI was characterized by intrinsic viscosity, solubility, FT‐IR , conductivity, SEM , and TGA measurements. The wide‐angle X ‐ray diffraction study revealed the appearance of a peak located at low angles (d = 29.4 – 35.3 Å) suggesting the formation of layered structure of PANI backbone separated by long alkyl side chains of DPA. The anticorrosive performance of the bilayer coatings composed of a bottom layer of DPA doped polyaniline covered with a polyvinyl butyral topcoat, have been demonstrated for steel exposed to neutral saline solutions. It was found that the inhibitive properties of DPA dopant provides further protection to the base metal through smart release when damage is produced on the surface of the coating. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1606–1616     

Synthesis and characterization of polyaniline doped with organic acids

Spectroscopic [UV–visible and Fourier transform IR (FTIR)] and thermal properties of chemically synthesized polyanilines are found to be affected by varying the protonation media (acetic, citric, oxalic, and tartaric acid). The optical spectra show the presence of a greater fraction of fully oxidized insulating pernigraniline phase in polyaniline doped with acetic acid. In contrast, the selectivity in the formation of the conducting phase is higher in oxalic acid as a protonic acid media. The FTIR spectra of these polymers reveal a higher ratio of the relative intensities of the quinoid to benzenoid ring modes in acetic acid doped polyaniline. Scanning electron micrographs revealed a sponge‐like structure derived from the aggregation of the small granules in acetic acid and oxalic acid doped polyaniline. A three‐step decomposition pattern is observed in all the polymers, regardless of the protonic acid used for the doping. The second step loss related to the loss of dopant is found to be higher in the oxalic acid doped polymer. In accordance with these results the conductivity is also found to be higher in oxalic acid doped material. The temperature dependent conductivity measurements show the thermal activated behavior in all the polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2043–2049, 2004     

Synthesis,Electrical Conductivity,Spectral and Thermal Stability Studies on Poly(aniline-co-o-nitroaniline)

o-Nitroaniline units were incorporated in the polyaniline backbone through copolymerization with aniline. The copolymers were synthesized for 1:3 and 1:1 molar ratios of aniline and o-nitroaniline in acidic medium using potassium persulphate as oxidant and their properties were compared with that of polyaniline. The polymers showed less electrical conductivity than polyaniline. Unlike polyaniline, the presence of nitro group caused higher frequency dependence of electrical conductivity. Electronic spectra showed a blue shift in both the band of the copolymers due to the decrease in the extent of conjugation leading to lower conductivity, which could also be explained in terms of a decrease of delocalization of electron as evinced from electron para magnetic resonance (EPR) data. Thermo gravimetric analysis (TGA) revealed that copolymer derived from 1:1 molar ratio showed comparable thermal stability with polyaniline and the one derived from 1:3 molar ratios is thermally less stable than polyaniline. Activation energies for thermal degradation were estimated using Broido equation. The temperature dependence of electrical conductivity suggested charge transport is mainly through variable range hopping.     

Polymer electrolyte membranes based on p‐toluenesulfonic acid doped poly(1‐vinyl‐1,2,4‐triazole): Synthesis,thermal and proton conductivity properties

Throughout this work, the synthesis, thermal as well as proton conducting properties of acid doped heterocyclic polymer were studied under anhydrous conditions. In this context, poly(1‐vinyl‐1,2,4‐triazole), PVTri was produced by free radical polymerization of 1‐vinyl‐1,2,4‐triazole with a high yield. The structure of the homopolymer was proved by FTIR and solid state ¹³C CP‐MAS NMR spectroscopy. The polymer was doped with p‐toluenesulfonic acid at various molar ratios, x = 0.5, 1, 1.5, 2, with respect to polymer repeating unit. The proton transfer from p‐toluenesulfonic acid to the triazole rings was proved with FTIR spectroscopy. Thermogravimetry analysis showed that the samples are thermally stable up to ～250 °C. Differential scanning calorimetry results illustrated that the materials are homogeneous and the dopant strongly affects the glass transition temperature of the host polymer. Cyclic voltammetry results showed that the electrochemical stability domain extends over 3 V. The proton conductivity of these materials increased with dopant concentration and the temperature. Charge transport relaxation times were derived via complex electrical modulus formalism (M*). The temperature dependence of conductivity relaxation times showed that the proton conductivity occurs via structure diffusion. In the anhydrous state, the proton conductivity of PVTri1PTSA and PVTri2PTSA was measured as 8 × 10^?4 S/cm at 150 °C and 0.012 S/cm at 110 °C, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1016–1021, 2010     

Structure–electrical property study of anisotropic polyaniline films

The relationships of the structure and electrical properties of anisotropic HCl‐doped polyaniline (PANI) films cast from N,N′‐dimethylpropylene urea (DMPU) solutions and stretched to different draw ratios were studied. The anisotropic structure of the stretched PANI films was examined by X‐ray diffraction, near‐infrared wave‐guide coupling, and polarized infrared measurements. The PANI emeraldine base (EB) films cast from DMPU solutions had a single‐phase noncrystalline structure, and stretching of the films did not cause crystallization to occur. The transition moment angles of two weakly absorbing infrared bands were determined, and the Hermans' orientation functions for the PANI EB films were calculated. The PANI films were then doped with HCl, and the electrical properties were determined by impedance spectroscopy. With a specially designed test fixture, the in‐plane and through‐plane impedance was obtained. The conductivity along the stretch direction increased with orientation. The in‐plane conductivity was significantly higher than the through‐plane conductivity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 823–841, 2003     

Synthesis and characterization of epoxidized polybutadiene/polyaniline graft conducting copolymer

In this article the synthesis and characterization of an elastomeric conducting material, obtained by grafting polyaniline (EB) on commercial cis‐1,4‐polybutadiene (PB), are described. PB was first partially epoxidized in chloroform solution using meta‐chloroperbenzoic acid (MCPBA). The conducting polymer was then grafted to the activated polybutadiene (EPB) via the aminolysis reaction between the polyaniline NH₂ terminal groups and the oxirane rings. The material so obtained (EPBPAN) and the epoxidized intermediate product were characterized by ¹H NMR, ¹³C NMR, Fourier transform infrared, and ultraviolet–visible spectroscopy, thermal and mechanical analysis, and electrical conductivity measurements. The effect of the sample deformation on conductivity also was analyzed. The HCl doping of the EPBPAN film induced crosslinking reactions, generated by the acid cleavage of unreacted oxirane groups. The electrical conductivity of the doped material reached values of about 10^?5 Ω^?1 cm^?1. The key characteristics of our elastomeric conducting material are its simple synthesis, its starting as a commercial product, and the solubility of its undoped form in a common low‐boiling organic solvent like chloroform. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3082–3090, 2004     

Infrared stealth and anticorrosion performances of organically modified silicate‐NiZn ferrite/polyaniline hybrid coatings

Hybrid coatings based on organically modified silicate‐Ni_0.5Zn_0.5Fe₂O₄/polyaniline were synthesized through a sol–gel technique with different NiZn ferrite/polyaniline weight ratio (1/1, 1/2, 1/5). These hybrid films were deposited via spin coating onto an aluminum alloy to improve the corrosion protection and to act as infrared stealth coatings. The effects induced by the NiZn ferrite/polyaniline hybrids on the chain dynamic, ferromagnetic behavior, infrared stealth, and anticorrosion performances of the coated samples were investigated. The rotating‐frame spin‐lattice relaxation times and scale of the spin‐diffusion path length indicated that the configuration of the hybrid films was highly cross‐linked and dense. The thermal extinction of the hybrid coatings increased with the increase in the polyaniline content. Potentio‐dynamic and salt‐spray analysis revealed that the hybrid films provided an exceptional barrier and corrosion protection in comparison with untreated aluminum alloy substrates. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 926–935, 2008     

Electrical and optical properties of ceramic–polymer nanocomposite coatings

Transparent, conductive composite coatings were fabricated from suspensions of poly(vinyl acetate‐acrylic) (PVAc‐co‐acrylic) copolymer latices (50–600 nm) and nanosized antimony‐doped tin oxide (ATO) particles (～15 nm). The suspensions were deposited as coatings onto poly(ethylene terephthalate) substrates and dried at 50 °C. Microstructure studies using field emission scanning electron microscopy and tapping‐mode atomic force microscopy (TMAFM) indicated that the latex particles coalesced during drying and forced the ATO particles to segregate into the boundaries between the latex particles. Low phase contrast was observed with TMAFM; this result was consistent with the presence of PVAc‐co‐acrylic in the ATO‐rich phase of the composite. The conductivity of the composite coatings followed a percolation power‐law equation, with the percolation threshold between 0.05 and 0.075 volume fractions of ATO and the critical conductivity exponent ranging from 1.34 to 2.32. The highest direct‐current conductivity of the composite coatings was around 10^?2 S/cm. The optical transmittance and scattering behavior of the coatings were also investigated. Compared with the PVAc‐co‐acrylic coating, the composite coatings had lower transparency because of the Rayleigh scattering. The transparency of the composite coatings was improved by a reduction in the coating thickness. The best transparency for the coatings with a direct‐current conductivity of approximately 10^?2 S/cm was around 85% at a wavelength of 600 nm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1744–1761, 2003     

Precipitation polymerization of aniline in the presence of water‐soluble organic acids

The precipitation polymerization of aniline in the presence of organic acids, including toluene‐4‐sulfonic acid, phenylphosphonic acid, 4‐aminophenylphosphonic acid, and acetophosphonic acid, led in one step to conductive polyaniline. The polyaniline showed very good affinity for water and was easily modified to be water‐soluble. In comparison with the widely studied postpolymerization of doped polyaniline, this reaction allowed reasonably good conductivity to be achieved at a lower acid/polyaniline ratio. Moreover, the easy in situ incorporation of the dopant into the polymer structure caused high stability of the created salt; that is, no dedoping was observed after it was washed with water, methanol, or other solvents. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3562–3569, 2002     

Morphological study on water‐borne conducting polyaniline‐poly(ethylene oxide) blends

Conducting polyaniline‐poly(ethylene oxide) blends were prepared from their aqueous solutions. The blends displayed an electrical conductivity percolation threshold as low as 1.83 wt % of polyaniline loading. As demonstrated by scanning electron microscopy, polarized optical microscopy, and wide‐angle X‐ray diffraction studies, the conducting polyaniline took a fibrillar morphology in the blend, and it existed only in the amorphous phase of poly(ethylene oxide). A three‐phase model combining morphological factors instead of a two‐phase model was proposed to explain the low‐conductivity percolation threshold. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 605–612, 2002; DOI 10.1002/polb.10114     

Synthesis and characterization of C60/polyaniline composites from interfacial polymerization

C₆₀/polyaniline (PANI) nanocomposites have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in the presence of C₆₀ by using an interfacial reaction. When compared with the pure PANI nanofibers from the similar process, the diameter of the obtained C₆₀/PANI nanofibers was increased because of the encapsulation of C₆₀ into PANI during aniline polymerization, which resulted from the charge‐transfer interactions between C₆₀ and aniline fragment in PANI. In addition, the resulting C₆₀/PANI nanocomposites synthesized from the low initial C₆₀/aniline molar ratio (less than 1:25) showed the homogenous morphology composed of fiber network structures, which has an electrical conductivity as high as 1.1 × 10^?4 S/cm. However, the C₆₀/PANI nanocomposites from the higher initial C₆₀/aniline molar ratio (more than 1:15) showed the nonuniformly distributed morphology, and the electrical conductivity was decreased to 3.5 × 10^?5 S/cm. Moreover, the C₆₀/PANI nanocomposites from the interfacial reaction showed a higher value of electrical conductivity than the mechanically mixed C₆₀/PANI blends with the same C₆₀ content, because of the more evenly distributed microstructures. FTIR, UV–vis, and CV data confirmed the presence of C₆₀ and the significant charge‐transfer interactions in the resultant nanocomposites, which was responsible for the morphology development of the C₆₀/PANI and the variation of the electrical conductivity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Conductivity and characterization of polyurea electrolytes with carboxylic acid

Polyurea, which was synthesized from 4,4′‐diphenylmethane diisocyanate, Jeffamine‐ED2001 (weight‐average molecular weight: 2000), and 3,5‐diaminobanzoic acid (DABA) were doped with lithium perchlorate (LiClO₄) as the polyelectrolyte. Differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, and ⁷Li magic‐angle spinning (MAS) solid‐state NMR were used to monitor changes in the morphology of polyurea electrolytes corresponding to the concentration of LiClO₄ dopants. DSC showed the glass‐transition temperature of the hard and soft segments increases with salt concentration. FTIR indicated the carboxylic group of DABA coordinates with the Li⁺ ion, and the ordered hydrogen‐bonded urea carbonyl groups are destroyed when the salt concentration exceeds 0.5 mmole of LiClO₄ (gPUrea)^?1. The ⁷Li MAS solid‐state NMR investigation of the polyurea electrolytes revealed the presence of two Li⁺ environments at lower temperature. Impedance spectroscopy measurements showed that the conductivity behavior followed the Arrhenius equation, and the maximum conductivity occurred when the crystalline structure of polyurea was disrupted. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 4007–4016, 2003     

Novel conducting polymer poly[bis(phenylamino)disulfide]: Synthesis,characterization, and properties

A bis(phenylamino)disulfide was prepared through the reaction of S₂Cl₂ with aniline, and its configuration was confirmed with elemental analysis, Fourier transform infrared (FTIR), Fourier transform Raman (FT‐Raman), and ¹H NMR spectroscopy. A novel conducting polymer, poly[bis(phenylamino)disulfide] (PPAD), was synthesized from bis(phenylamino)disulfide by both chemical and electrochemical polymerization. The structure of this polymer, in which the side‐chain disulfide bonds were linked to the nitrogen atoms of the main‐chain polyaniline, was characterized with FTIR, FT‐Raman, gel permeation chromatography, electron spectroscopy, and X‐ray photoelectron spectroscopy. A four‐probe measurement revealed that the electrical conductivity of PPAD was 1.8 × 10^?2 to 2.1 × 10^?3 S cm^?1, depending on the doping agents and the pH of the medium for either chemical synthesis or electrochemical synthesis. The conductivity, molecular weight, and spectroscopic properties of the polymer, in comparison with those of polyaniline, showed decreases in the polaron delocalization, structural order, and doping level of the main chain because of the steric hindrance of side‐chain S? S bonds. The cyclic voltammograms of the polymer and the monomer showed that the redox reactions (doping/undoping processes) of the main chain (π‐conjugated system) occurred in almost the same potential range of ?0.3 to 0.3 V versus an Ag/AgCl (saturated KCl) electrode as that of thiol (thiolate anion)/disulfide of the side chain in PPAD; the bond cleavage (reduction) and formation (oxidation) reactions of the disulfide bond in the polymer became easier and more reversible than those of the monomer. These results suggested that this conducting organodisulfide polymer might be a candidate material for energy‐storage devices such as lithium secondary batteries, proton‐exchange batteries, and electrochemical capacitors. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2329–2339, 2004     

A new route to obtain PVDF/PANI conducting blends

Electrically conductive poly(vinylidene fluoride)(PVDF) - polyaniline blends of different composition were synthesized by chemical polymerization of aniline in a mixture of PVDF and dimethylformamide (DMF) and studied by electrical conductivity measurement, UV-Vis-NIR and FTIR spectroscopy. The samples were obtained as flexible films by pressing the powder at 180 °C for 5 min. The electrical conductivity showed a great dependence on the syntheses parameters. The higher value of the electrical conductivity was obtained for the oxidant/aniline molar ratio equal to 1 and p-toluenesulfonic acid-TSA/aniline ratio between 3 and 6. UV-Vis-NIR and FTIR spectra of the blend are similar to the doped PANI, indicating that the PANI is responsible for the high electrical conductivity of the blend. The electrical conductivity of blend proved to be stable as a function of temperature decreasing about one order at temperature of 100 °C. The route used to obtain the polymer blend showed to be a suitable alternative in order to obtain PVDF/PANI-TSA blends with high electrical conductivity.     

Effect of oxidant on electronic transport in polypyrrole nanotubes synthesized in the presence of methyl orange

Polypyrrole nanotubes with diameter 60–400 nm are synthesized with methyl orange as template and various oxidants, iron(III) chloride hexahydrate, iron(III) sulfate hydrate, and ammonium peroxydisulfate. The highest electrical conductivity of compressed pellets, 66 S cm^?1, is found for iron(III) chloride. Regions with 3D variable range hopping in series with ordered regions near metal–insulator transition govern the charge transport. Other oxidants and globular morphology provide less conducting samples, <10 S cm^?1. The transport mechanism is identified with the heterogeneous model of tunneling between (bi)polaronic clusters with parallel contribution of Arrhenius‐like activated conductivity. The results of conductivity are correlated with the protonation level reflected in the infrared spectra and with the ratio of bipolaron/polaron bands revealed by Raman spectroscopy. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1147–1159     

Effect of acidification treatment and morphological stability of sulfonated poly(arylene ether sulfone) copolymer proton‐exchange membranes for fuel‐cell use above 100 °C

Directly copolymerized wholly aromatic sulfonated poly(arylene ether sulfone) copolymers derived from 4,4′‐biphenol, 4,4′‐dichlorodiphenyl sulfone, 3,3′‐disulfonated, and 4,4′‐dichlorodiphenyl sulfone (BPSH) were evaluated as proton‐exchange membranes for elevated temperature operation (100–140 °C). Acidification of the copolymer from the sulfonated form after the nucleophilic step (condensation) copolymerization involved either immersing the solvent‐cast membrane in sulfuric acid at 30 °C for 24 h and washing with water at 30 °C for 24 h (method 1) or immersion in sulfuric acid at 100 °C for 2 h followed by similar water treatment at 100 °C for 2 h (method 2). The fully hydrated BPSH membranes treated by method 2 exhibited higher proton conductivity, greater water absorption, and less temperature dependence on proton conductivity as compared with the membranes acidified at 30 °C. In contrast, the conductivity and water absorption of a control perfluorosulfonic acid copolymer (Nafion 1135) were invariant with treatment temperature; however, the conductivity of the Nafion membranes at elevated temperature was strongly dependent on heating rate or temperature. Tapping‐mode atomic force microscope results demonstrated that all of the membranes exposed to high‐temperature conditions underwent an irreversible change of the ionic domain microstructure, the extent of which depended on the concentration of sulfonic acid sites in the BPSH system. The effect of aging membranes based on BPSH and Nafion at elevated temperature on proton conductivity is also discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2816–2828, 2003