Nonuniform distribution of the ionogenic groups in permselective membranes

The nonuniformity of the distribution of ionogenic groups in various ion exchange membranes as NAFION, MRF, IONAC and PE-PSSA was evaluated according to Glueckauf's theory. For this purpose the nonuniformity factor Z was estimated on the base of the sorption of sulphuric acid for the PE-PSSA membranes on the quantitative elaboration of the microautoradiographs. Both methods give similar results which confirm Glueckauf's theory and prove the applicability of the microautoradiographic method for a quantitative determination of the membrane nonuniformity. It was found, that the nonuniformity factor depends on the content of the crosslinking agent, whereas its value does not depend distinctly on the chemical composition of the membranes.     

Analysis of radiation-grafted membranes for fuel cell electrolytes

One of the primary obstacles to be overcome for the development of economical fuel cells is the high cost of the membrane electrolyte. The currently favoured polymer electrolytes consist of poly(tetrafluoroethylene) backbone structures and poly(perfluorosulphonic acid) side chains. In an effort to find lower cost membranes, some radiation-grafted copolymer membranes were investigated. All the membranes contained poly(styrenesulphonic acid) side chains. Three different backbone polymer structures were studied: low-density poly(styrene), poly(tetrafluoroethylene)/poly(perfluoropropylene), and poly(tetrafluoroethylene). The results indicate that the membrane consisting of a poly(tetrafluoroethylene)/poly(styrenesulphonic acid) copolymer is a promising candidate as a fuel-cell electrolyte.     

Complex dielectric permittivity of an ion-containing polymer in the microwave region

A method for determination of the complex dielectric permittivity of polar, non-polar and ion-containing polymers at microwave frequencies is presented. Disk-shaped samples are employed in a radial-line configuration at the end of a coaxial-line structure. An equivalent circuit, established by admittance measurements, is used to relate the capacitance at the sample face to the impedance measured on the slotted line preceding the coaxial sample holder. The method has been applied first to determine the frequency spectrum of polyethylene (PE) and poly(tetrafluoroethylene) (PTFE) between 80 MHz and 4 GHz at 293 K. The results agree with those reported in the literature, demonstrating the reliability of the method as well as usability of PE and PTFE as standards at high frequencies. Subsequently, the AMF C-311 cation exchange membrane (polyfluorocarbon backbone chains with grafted polystyrene side chains containing sulfonate groups) was studied in the same frequency range. Values of dielectric permittivity and dielectric losses for AMF C-311 samples in the dry and swollen hydrated states are reported and compared.     

Polyacrylonitrile‐based proton conducting membranes containing sulfonic acid and tetrazole moieties

Proton conducting membranes based on polymers containing sulfonic acid and tetrazole moieties were developed. Successful syntheses of poly(acrylonitrile‐co ‐styrene sulfonic acid) (PAN‐co ‐PSSA), poly(acrylonitrile‐co ‐5‐vinyl tetrazole) (PAN‐co ‐PVTz), and poly(acrylonitrile‐co ‐5‐vinyl tetrazole‐co ‐styrene sulfonic acid) (PAN‐co ‐PVTz‐co ‐PSSA) were confirmed by ¹H‐nuclear magnetic resonance spectroscopy, elemental analysis, and Fourier transform infrared spectroscopy. Two approaches were performed to study the effects of molar ratio of sulfonic acid to tetrazole and tetrazole content on membrane properties. In the first approach, PAN‐co ‐PSSA was blended with PAN‐co ‐PVTz at three molar ratios. The second approach focused on PAN‐co ‐PVTz‐co ‐PSSA membranes with various tetrazole contents. PAN‐co ‐PSSA membrane was also prepared. All solution‐cast membranes were hydrolytically stable, except for PAN‐co ‐PVTz‐co ‐PSSA with 71% tetrazole. Surface morphologies of blend membranes were studied using scanning electron microscopy, and no phase separation was observed. Water uptake was shown to increase with increasing tetrazole. All membranes exhibited high thermal stability (up to 250 °C) and high storage moduli. Proton conductivity was found to depend significantly on relative humidity. The influences of sulfonic acid to tetrazole ratio and tetrazole content on proton conduction were observed and discussed. A maximum proton conductivity of 7.1 × 10^?3 S/cm at 26 °C was obtained from PAN‐co ‐PSSA membrane. In addition, all tested membranes showed relatively good oxidative stability after treatment in Fenton's reagent. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45411.     

Preparation and characterization of proton conducting polysulfone grafted poly(styrene sulfonic acid) polyelectrolyte membranes

The syntheses of series of proton conducting comb copolymer membrane involving polysulfone back bone as main chain and poly(styrene sulfonic acid) (PSSA) being side chain, i.e. polysulfone grafted poly(styrene sulfonic acid) (PSU-g-PSSA) are presented. Chloromethylation of the polysulfone backbone was done by Fridel Craft alkylation reaction. Atom transfer radical polymerization was used for control grafting from the chloromethylated positions. The successful substitution of the chloromethyl group and its grafting with PSSA was characterized by elemental analysis and proton nuclear magnetic resonance. Water uptake, electrochemical properties like ion exchange capacity (IEC) and proton conductivities increase with increase in PSSA contents. Thermal gravimetric analysis (TGA) showed the thermal stability of membranes up to 250 °C. Proton conductivity for maximum amount of grafting is 0.02 S/cm.     

Specific resistances of hydrophilic membranes containing ionogenic groups

This paper deals with an investigation of the dependence of specific resistances on pH for hydrophilic membranes containing ionogenic groups. Membranes based on poly(2-hydroxyethyl methacrylate) crosslinked with ethylene dimethacrylate were investigated. This basic structure was modified by copolymerization with ionogenic comonomers, i.e., methacrylic acid and/or diethylaminoethyl methacrylate. It is shown that the dependence of the specific resistance on pH passes through a maximum for cation-active membranes at pH ～ 3.5, for anion-active membranes at pH ～ 10, and for ampholytic membranes at pH ～ 6. The effect of the content of ionogenic groups, network density, and the degree of neutralization of membranes on the above dependence is discussed. In the final part of the paper the results are compared with more hydrophilic systems based on poly(2-hydroxyethyl acrylate) and it is shown that maxima in the dependence of specific resistances on pH can be suppressed by increasing the hydrophilicity of polymers.     

Pore model parameters of cation-exchange membranes

Parameters of the equivalent pore model of different membranes (NAFION-125, MRF-26, and the polyethylene-polystyrenesulphonic acid membranes (PE/PSSA)) were estimated from measurements of water hydraulic permeabilities. The pore radius calculations were performed according to the modified Ferry-Elford equation r_θ = r_FEθ, where r_FE is the radius calculated from the Ferry-Elford relation and Å the tortuosity factor. The PE/PSSA membranes, expanded in hot water, were similar to the MRF-26 membranes in their equivalent pore model parameters (radius 20 – 24 Å, and specific permeation rate 5.09 and 4.30.10^?16 cm², respectively). The NAFION-125 membrane exhibits the smallest pore radius (14 Å) and specific permeation rate (0.841·10^?16 cm²).     

Development of stable and active PVA‐PSSA/SA‐PVA catalytic composite membrane for esterification enhancement

An active and stable catalytic composite membrane (CCM), poly(vinyl alcohol)–poly(styrene sulfonic acid)/sodium alginate–poly(vinyl alcohol) (PVA‐PSSA/SA‐PVA), was prepared to enhance the esterification of ethanol and propionic acid. The morphologies and crystal structures of the CCMs were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, and X‐ray diffraction. The effects of catalytic layer thickness, mass ratio of PVA to PSSA, concentration of catalytic layer solution, ratio of reaction volume to membrane area, and molar ratio of propionic acid to ethanol were discussed. The pervaporation results showed that the flux of CCM increased from 118 to 320 g m^?2 h^?1 compared with the SA‐PVA membrane because of the close affinity and low resistance of PSSA to water. After crosslinking with 3‐aminopropylmethyldiethoxysilane, the CCMs had good catalytic activities. The acid conversion reached 92.8% at 75 °C in 12 h, and the stabilization of the CCM was greatly improved. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46514.     

Water in different poly(styrene sulfonic acid)‐grafted fluoropolymers

We investigated the water present in a series of radiation‐grafted fluoropolymers with similar poly(styrene sulfonic acid) (PSSA) contents with the aim of determining the influence of the initial fluoropolymer. Radiation‐grafted membranes were compared with Nafion 117 and 105. Sorption curves and differential scanning calorimetry thermograms showed that all the membranes contained the same number of water molecules tightly bound to the sulfonic acid groups; this water did not freeze. In radiation‐grafted membranes, the content of freezing water absorbed from the liquid‐phase water varied according to the swelling abilities of the membrane, which were dependent on the initial fluoropolymer. Larger pores accompanied high water uptakes and high conductivity. The amount of water absorbed from the vapor phase was similar for all radiation‐grafted membranes with similar PSSA contents, irrespective of matrix material. Nafion membranes had higher conductivities at intermediate hydration levels, and the relaxation times measured by NMR were longer than for the radiation‐grafted materials. This suggests that the channels for water and proton conduction are different in the two types of materials. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 33–42, 2002     

Preparation and characterization of PSSA/PVA catalytic membrane for biodiesel production

Poly(styrene sulfonic acid) (PSSA)/Poly(vinyl alcohol) (PVA) blend membranes prepared by the solution casting were employed as heterogeneous acid catalysts for biodiesel production from acidic oil obtained from waste cooking oil (WCO). The membranes were annealed at different temperature in order to enhance their stability. The structure and properties of the membranes were investigated by means of Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), X-ray diffraction (XRD). It is found that the crosslinking structure among PVA and PSSA chains formed when the thermal treatment temperature was higher than 80 °C. The retention of PSSA in the blend membranes in the methanol/water solvent was markedly increased from 50% to 85% with the increase of the annealing temperature from room temperature (for the untreated membrane) to 150 °C due to the formation of the crosslinking structure. The results of esterification of acidic oil show that the conversion was slightly improve with the PVA content in the membrane at a fixed PSSA content. The thickness of the catalytic membrane had no significant effect on the conversion in the end. The membrane annealed at 120 °C exhibited the best catalytic performance among the membranes, with a stable conversion of 80% with the runs.     

Preparation and characterization of layered membranes constructed by sequential redox‐initiated grafting onto polyacrylonitrile ultrafiltration membranes

Layered membranes were prepared by sequential grafting—by means of redox initiators—of water‐soluble monomers, with oppositely charged ionic groups, onto ultrafiltration (UF) polyacrylonitrile (PAN) membranes at room temperature. Grafting of a single layer of 2‐hydroxyethylmethacrylate (HEMA) onto a PAN membrane gave a highly grafted membrane with a relatively high water flux. Bilayered membranes with various properties containing poly‐2‐(dimethylamino)ethyl methacrylate (p‐2DMAEMA) as the bottom layer and polymethacrylic acid or polystyrenesulfonic acid (p‐SSA) as the upper layer were prepared and compared—by means of infrared spectroscopy and electron microscopy—with single‐layered membranes of grafted polyhydroxyethylmethacrylate. Layered membranes exhibited a significant decline in water flux in comparison with the initial UF membranes. The flux could, however, be manipulated by controlling the concentration of monomers, the time of grafting, and the number of layers. When four layers of p‐2DMAEMA and p‐SSA were sequentially grafted onto a PAN membrane, pure water fluxes were stable over a wide range of pH values and did not change over long storage times. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 509–520, 2005     

Effect of dietary fat on phospholipid class distribution and fatty acid composition in rat fat cell plasma membrane

The effect of dietary fats on phospholipid class distribution and fatty acid composition was studied in rat fat cell plasma membrane. Three groups of male Wistar weanling rats were fed for 8 wk three diets differing in the amount and nature of the fats: 1.5% sunflower oil (low fat control; LFC), 10% sunflower oil (high fat, unsaturated; HFU), 1.5% sunflower oil+8.5% cocoa butter (high fat, saturated; HFS). Plasma membranes were prepared from epididymal adipocytes. The amount and type of dietary fat significantly altered membrane phospholipid distribution. Phospholipid content was lowered with HFU as compared to LFC or HFS diets, but no changes were observed for cholesterol. Phosphatidylinositol (PI) and phosphatidylserine (PS) were less affected by dietary changes than were other phospholipid classes. Major changes were detected for phosphatidylcholine (PC), phosphatidylethanolamine (PE) and sphingomyelin (SM) contents. No large changes in PC and PE fatty acid compositions were observed between the LFC and HFS groups, but the HFU diet induced several changes. Correlations with plasma membrane 5′-nucleotidase activities are discussed.     

Viscosimetric study of poly(vinyl alcohol)/poly(styrenesulfonic acid) miscibility in dilute aqueous solution

The miscibility of poly(vinyl alcohol) (PVA) and poly(styrenesulfonic acid) (PSSA) in dilute aqueous solutions was studied by a viscosimetric method. At a constant molecular weight of PSSA, it was found that the miscibility of both polymers increases with the molecular weight and the number of acetate groups of the PVA samples (1 and 12% unhydrolyzed sites). Moreover, this miscibility increases slightly with the total mixture concentration in the interval 1–2 g/dL. By comparison of the results of reduced viscosity of PVA/PSSA and PVA/poly(sodium styrenesulfonate) (PSSNa) mixtures, it has been deduced that the miscibility of two polymers is due mainly to intermolecular interactions between the hydroxyl and sulfonic groups of PVA and PSSA, respectively. These groups act as acceptors and donors of hydrogen bonds which are the responsible for polymers' miscibility. © 1996 John Wiley & Sons, Inc.     

Electrochemical properties of polyethylene membrane modified with sulfonic and phosphonic acid groups

Ion-exchange membranes modified with sulfonic (-SO₃H) and phosphonic acid (-PO₃H) groups were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polyethylene (PE) films and sub-sequent sulfonation and phosphonation of poly(GMA) graft chains. The surface area, thickness and volume of grafted PE film increased with increasing grafting yield. The specific electrical resistance of PE membrane modified with the -PO₃H and -SO₃H groups decreased with increasing the ion-exchange capacity. The PE membrane modified with -PO₃H group had a lower specific electrical resistance than that of PE membrane modified with -SO₃H group.     

Synthesis and characterization of poly(ether sulfone) grafted poly(styrene sulfonic acid) for proton conducting membranes

Two-step synthesis of proton-conducting poly(ether sulfone) (PES) graft copolymer electrolyte membrane is proposed. Fridel Craft alkylation reaction was used to introduce chloromethyl pendant group onto the PES polymer backbone. Later on, atom transfer radical polymerization (ATRP) was applied to synthesize a series of poly(ether sulfone) grafted poly(styrene sulfonic acid) (PES-g-PSSA). Successful chloromethyl substitution and grafting of the pendant group was characterized by the ¹H-NMR and elemental analysis. Electrochemical properties such as ion exchange capacity (IEC), water uptake and proton conductivity increased with increasing PSSA contents. Thermal gravimetric analysis (TGA) showed the thermal stability of membranes up to 270 °C. Proton conductivity for maximum amount of grafting was 0.00297 S/cm.     

Synthesis and characterization of poly(2‐ethylaniline)–poly(styrenesulfonic acid) and poly(o‐phenetidine)–poly(styrenesulfonic acid) complexes

This research focuses on the synthesis of ethyl and ethoxy substituted polyaniline with poly(styrenesulfonic acid) comprising a poly(o‐phenetidine)–poly(styrenesulfonic acid) [P(O? P)‐PSSA] and poly(2‐ethylaniline)–poly(styrenesulfonic acid) [P(2‐E)‐PSSA]. The complexes P(O? P)‐PSSA and P(2‐E)‐PSSA were prepared by chemical polymerization of monomer (o‐phenetidine, 2‐ethylaniline) with PSSA using an oxidant of ammonium persulfate in 1M HCl solution; polyaniline (PANI), poly(2‐ethylaniline) (P2E), poly(o‐pheneditine) (POP), and polyaniline‐poly(styrenesulfonic acid) (PANI‐PSSA) also were prepared by chemical polymerization to be the reference samples. The products were characterized by IR, VIS, EPR, water solubility, elemental analysis, conductivity, SEM, and TEM. IR spectral studies shown that the structure of P(2‐E)‐PSSA and P(O? P)‐PSSA complexes is similar to that of polyaniline. EPR and visible spectra indicate the formation of polarons. The morphology of the blend was investigated by measured SEM and TEM, indicating the conducting component and electrically conductive property of the polymer complexes. The pH value for deprotonation [pH ≥ 9.5 for P(2‐E)‐PSSA and pH ≥ 8.0 for P(O? P)‐PSSA] are higher than that of corresponding HCl salts, indicating an intimate interaction between polymer chains. Elemental analysis results show that P(O? P)‐PSSA has a nitrogen‐to‐sulfur ratio of ～52%, larger than that for P(2‐E)‐PSSA, ～41%. The conductivity of the complexes is around 10^?2S/cm, and the solubility of P(2‐E)‐PSSA and P(O? P)‐PSSA in water is 2.9 and 1.9 g/L, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1198–1205, 2005     

Using Atom Transfer Radical Polymerization for the Synthesis of Grafted PVDF Copolymers towards the Synthesis of Membranes

Graft copolymers of poly(vinylidene fluoride) (PVDF) with poly(3-sulfopropyl methacrylic acid) (PVDF-g-PSPMA), poly(styrene-4-sulfonic acid) (PVDF-g-PSSA), and poly(dimethylaminoethyl methacrylate) (PDVFg-PDMAEMA) were synthesized. The aforementioned grafted copolymers were prepared from the corresponding (PDVF-g-PSPMPS) poly(3-sulfopropyl methacrylate potassium) and (PVDF-g-PSSS) poly(styrene-4-sulfonate sodium) salts using PVDF as a macroinitiator for atom transfer radical polymerization (ATRP). The copolymers were casted into membranes by the phase inversion method in aqueous media. The effects of polymerization time, degree of conversion, chain transfer agent (CTA) additive, crosslink process, and various solvents were investigated. The products were characterized by ¹H and ¹³C NMR spectroscopy, IR spectroscopy, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The maximum grafting incorporation was up to 26, 20 and 20 wt % for PSSA, PSPMA and PDMAEMA, respectively. The incorporation was reduced using a CTA additive. The most impressive feature of the graft copolymer membranes produced in this study are the improved water fluxes and polyethylene glycol (PEG) rejection properties when compared to the commercially available, pristine PVDF.     

Electrospun composite nanofibers of poly (vinylidene fluoride‐trifluoroethylene)/polyaniline‐polystyrene sulfonic acid

Nanofibers of poly(vinylidene fluoride‐trifluoroethylene)/polyaniline‐polystyrene sulfonic acid (PVDF‐TrFE/PANi‐PSSA) were fabricated in air at room temperature using electrospinning, with the thinnest fiber having a diameter of ～ 6 nm. This is a cheap, fast, and reliable process for generating PVDF‐TrFE/PANi‐PSSA composite nanofibers. The presence of conducting PANi‐PSSA increased the charge density of the solution and assisted in the fabrication of PVDF‐TrFE nanofibers at low polymer concentrations in dimethylformamide without the beading effect. Ultraviolet and visible spectroscopy showed that PANi‐PSSA was well incorporated into the PVDF‐TrFE solution with no polymer segregation or degradation. A scanning electron microscope was used for morphological characterization of the fibers and a profilometer used to determine the fiber diameter. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel self‐supported natural and synthetic polymer membranes for air humidification

Novel self‐supported natural and synthetic polymer membranes of chitosan‐hydroxy ethyl cellulose‐montmorillonite (CS‐HEC‐MMT) and polyvinyl alcohol (PVA)‐polystyrene sulfonic acid (PSSA) are prepared by solution casting method followed by crosslinking. These membranes are employed for air humidification at varying temperatures between 30°C and 70°C and their performances are compared with commercial Nafion^® membranes. High water fluxes with desired humidified‐air output have been achieved for CS‐HEC‐MMT and PVA‐PSSA hybrid membranes at air‐flow rates of 1–10 slpm. Variation in the air/water mixing ratio, dew point, and relative humidity that ultimately results in desired water flux with respect to air‐flow rates are also quantified for all the membranes. Water flux values for CS‐HEC‐MMT are less than those for Nafion^® and PVA‐PSSA membranes, but the operational stability of CS‐HEC‐MMT membrane is higher than PVA‐PSSA and comparable with Nafion^® both of which can operate up to 70°C at repetitive cycles of humidification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrochemical behaviors of polyaniline–poly(styrene‐sulfonic acid) complexes and related films

This research focuses on the syntheses of polyaniline with poly(styrenesulfonic acid) and their electrochemical behavior, including absorbance behavior and electrochemical response time of polyaniline‐poly(styrenesulfonic acid) [PANI–PSSA]. The complexes PANI–PSSA were prepared by electrochemical polymerization of monomer (aniline) with PSSA, using indium‐tin oxide (ITO) as working electrode in 1M HCl solution. Polyaniline (PANI), poly(o‐phenetidine)–poly(styrenesulfonic acid) [POP–PSSA], and poly(2‐ethylaniline)–poly(styrenesulfonic acid) [P2E‐PSSA] also were prepared by electrochemical polymerization and to be the reference samples. The products were characterized by IR, VIS, EPR, water solubility, elemental analysis, conductivity, SEM, and TEM. IR spectral studies shows that the structure of PANI–PSSA complexes is similar to that of polyaniline. EPR and visible spectra indicate the formation of polarons. The morphology of the blend were investigated by SEM and TEM, which indicate the conducting component and electrically conductive property of the polymer complexes. Elemental analysis results show that PANI–PSSA has a nitrogen to sulfur ratio (N/S) of 38%, lower than that for POP–PSSA (52%) and P2E–PSSA (41%). Conductivity of the complexes are around 10^?2 S/cm, solubility of PANI–PSSA in water is 3.1 g/L. The UV‐Vis. absorbance spectra of the hybrid organic/inorganic complementary electro‐chromic device (ECD), comprising a polyaniline–poly(styrenesulfonic acid) [PANI–PSSA] complexes and tungsten oxide (WO₃) thin film coupled in combination with a polymer electrolyte poly(2‐acrylamido‐2‐methyl‐propane‐sulfonic acid) [PAMPSA]. PANI–PSSA microstructure surface images have been studied by AFM. By applying a potential of ～3.0 V across the two external ITO contacts, we are able to modulate the light absorption also in the UV‐Vis region (200–900 nm) wavelength region. For example, the absorption changes from 1.20 to 0.6 at 720 nm. The complexes PANI–PSSA, POP–PSSA, and P2E–PSSA were prepared by electrochemical polymerization of monomer (aniline, o‐phenetidine, or 2‐ethylaniline) with poly(styrenesulfonic acid), using ITO as working electrode in 1M HCl solution, respectively. UV‐Vis spectra measurements shows the evidences for the dopped polyaniline system to be a highly electrochemical response time, recorded at the temperature 298 K, and the results were further analyzed on the basis of the color‐ discolor model, which is a typical of protontation systems. Under the reaction time (3 s) and monomer (aniline, o‐phenetidine, 2‐ethylaniline) concentration (0.6M) with PSSA (0.15M), the best electrochemical color and discolor time of the PANI–PSSA is slower than POP–PSSA complexes (125/125 ms; thickness, 3.00 μm) and P2E–PSSA complexes. Under the same thickness (10 μm), the best electrochemical color and discolor time of the PANI–PSSA complexes is 1500/750 ms, that is much slower than P2E–PSSA complexes (750/500 ms) and POP–PSSA complexes (500/250 ms). In film growing rate, the PANI–PSSA complexes (0.54 μm/s) are slower than P2E–PSSA complexes (0.79 μm/s) and POP–PSSA complexes (1.00 μm/s), it can be attributed to the substituted polyaniline that presence of electro‐donating (? OC₂H₅ or ? C₂H₅₎ group present in aniline monomer. The EPR spectra of the samples were recorded both at 298 K and 77 K, and were further analyzed on the basis of the polaron–bipolaron model. The narrower line‐width of the substituted polyaniline complexes arises due to polarons; i.e., it is proposed that charge transport take place through both polarons and bipolarons, compared to their salts can be attributed to the lower degree of structural disorder, the oxygen absorption on the polymeric molecular complexes, and due to presence of electro‐donating (? OC₂H₅ or ? C₂H₅) group present in aniline monomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:4023–4044, 2006