Dual functionality of PTSA as electrolyte and dopant in the electrochemical synthesis of polyaniline,and its effect on electrical properties

The electrochemical synthesis of polyaniline (PAni) powder was carried out from an aqueous solution of 0.15 mol L^?1 aniline with varying concentrations of p‐toluenesulphonic acid (PTSA) at room temperature. The PAni samples thus obtained were characterized using DC and AC conductivity, dielectric properties, infrared spectroscopy, thermogravimetric analysis, X‐ray analysis, scanning electron microscopy and ultraviolet spectroscopy. Results showed that PTSA is acting both as electrolyte and doping agent. With an increase in the PTSA concentration, there is more polaron formation, and this means an increase in charge carrier concentration and mobility. This accounts for the increase in conductivity and improved dielectric properties of the resultant PAni. The polymer was subjected to a heating and cooling cycle. The change in conductivity during the heating cycle is quite different from that during the cooling cycle, indicating some kind of hysteresis phenomenon occurring in the system. Moreover there is a net decrease in room temperature conductivity of PAni when subjected to the heating–cooling cycle. This may be due to the oxidation of PAni and generation of some kind of disorder in the structure of PAni during the heating–cooling process. Copyright © 2007 Society of Chemical Industry     

Corrosion-free electrochemical synthesis of polyaniline using Cu counter electrode in acidic medium

Polyaniline (PAni) was electrochemically synthesized from aniline sulfate (AS) in the presence and in absence of H₂SO₄ using Cu counter electrode. No significant corrosion of the Cu electrode was found while synthesizing from AS in presence of H₂SO₄, whereas relatively higher corrosion of Cu as well as contamination of synthesized PAni with corroded Cu were observed for the synthesis from aniline in presence of H₂SO₄ or from AS in the absence of H₂SO₄. Corrosion-free synthesis yields PAni free from contamination of Cu and exhibits smaller particle size and superior electrical and supercapacitive behavior compared to the process exhibiting corrosion of counter electrode.     

Silica–polyaniline hybrid materials prepared by inverse emulsion polymerization for epoxy‐based anticorrosive coating

Polyaniline doped with dodecylbenzene sulfonic acid (PAni.DBSA) was prepared by inverse emulsion polymerization of aniline in toluene medium in the presence of silica (SiO₂) nanoparticles. The presence of cetyltrimethylammonium bromide (CTAB) during the aniline polymerization results in hybrid material with smaller particle size, as indicated by dynamic light scattering analysis and scanning electron microscopy. Also the electrical conductivity of such hybrid is one order higher, as compared with that prepared without CTAB. Moreover, more ordered PAni chain is obtained as indicated by the red shift of the π–polaron transition band observed by UV–vis spectroscopy and higher crystallinity observed by X‐ray diffraction analysis. Anti‐corrosive properties of carbon steel substrate coated with epoxy resin containing 5 wt % of PAni.DBSA and the corresponding SiO₂‐based hybrid materials were evaluated in 3.5% NaCl solution by electrochemical impedance spectroscopy. The coating resistance increases by one order for the epoxy system containing PAni.DBSA/SiO₂ hybrid prepared in the presence of CTAB, thus confirming the anticorrosion efficiency of this hybrid. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45505.     

Synthesis and properties of oxalic acid-doped polyaniline

Conductive polyaniline was synthesized in aqueous 1.0M oxalic acid containing 0.1 M aniline by electrochemical and chemical oxidation and characterized by conductivity, solubility, ultraviolet and infrared spectroscopy, and cyclic voltammetry. The solubility experiments showed that the solubility of oxalic acid-doped polyaniline in dimethylsulfoxide and dimethylformaide increased to a certain extent. The soluble part of the polyaniline was free from impurities such as quinones. Cyclic voltammetric studies in oxalic acid medium revealed that aniline exhibited a similar behaviour to that in H₂SO₄ and the polymerization rate was much slower than that in H₂SO₄.     

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     

Role of dual dopants in highly ordered crystalline polyaniline nanospheres: Electrode materials in supercapacitors

Aniline is oxidized by ammonium persulfate oxidant with a weak organic acid, 1,3‐(6,7)‐napthalene trisulfonic acid (NTSA), via an aqueous polymerization pathway to polyaniline (PANI) salt. The effects of the sodium lauryl sulfate surfactant, mineral acid [sulfuric acid (H₂SO₄)], and a combination of surfactant with mineral acid in the aniline polymerization reaction are also carried. These salts were designated as PANI–NTSA–dodecyl hydrogen sulfate (DHS), PANI–NTSA–H₂SO₄, and PANI–NTSA–DHS–H₂SO₄, respectively. Interestingly, PANI–NTSA–DHS showed a highly ordered crystalline sample with a nanosphere morphology. These PANIs were used as electrode materials in supercapacitor applications. Among the four salts, the PANI–NTSA–DHS–H₂SO₄ material showed higher values of specific capacitance (520 F/g), energy (26 W h/kg), and power densities (200 W/kg) at 0.3 A/g. Moreover, 77% of the original capacitance was retained after 2000 galvanostatic charge–discharge cycles with a Coulombic efficiency of 98–100%. PANI–NTSA–DHS–H₂SO₄ was obtained in excellent yield with an excellent conductivity (6.8 S/cm) and a thermal stability up to 235°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42510.     

Conductive composites from polyaniline and polyurethane sulphonate anionomer

The present work describes the synthesis of conductive composite of polyurethane sulphonate anionomer (PUSA) and para toluene sulphonic acid doped polyaniline (PANI–PTSA). HCl‐doped PANI was synthesized by chemical oxidative polymerization of aniline in HCl, which was converted to PANI–EB by treatment with NH₄OH. PTSA doped PANI was synthesized from EB‐PANI by redoping with PTSA solution. PUSA was synthesized from 4, 4′‐diphenylmethanediisocyanate (MDI), polypropylene glycol (PPG), 1,4‐butanediol (BD), and ionic diol SDOL. The composite was prepared by mixing of the solutions of two polymer components in DMF and then solution casting. The products were characterized and analyzed by UV‐Vis and FTIR spectroscopy, thermogravimetry, differential scanning calorimetry and scanning electron microscopy. The conductivity was found to increase by 100 times with concomitant decrease in percolation threshold when polyurethane was replaced by PUSA in the composite for the same amount of polyaniline. The composite film was thermally stable upto ～300°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41600.     

Synthesis and characterization of water‐soluble conducting polyaniline by enzyme catalysis

Enzymatic synthesis of a water‐soluble, conducting polyaniline (PANI) was studied, using horseradish peroxidase as the biocatalyst and H₂O₂ as the initiator, in the presence of a poly(vinylsulfonic acid, sodium salt) (PVS) polyanion template. The effects of the buffer, concentration of H₂O₂, and the molar ratio of aniline to PVS on the polymerization were particularly investigated. The products were characterized by UV–vis/near‐IR and FTIR spectroscopy, thermogravimetric analysis, and four‐point probe conductivity measurement. The results showed that PVS could be chosen as a new template in the synthesis of PANI. The proper conditions of polymerization were obtained as follows: pH of the buffer was pH 4.0–5.0, the concentration of H₂O₂ was around 20 mM, and the molar ratio of PVS to aniline was 1–1.5. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 814–817, 2005     

Poly(vinylidene fluoride-co-hexafluorpropylene)/polyaniline conductive blends: Effect of the mixing procedure on the electrical properties and electromagnetic interference shielding effectiveness

Poly(vinylidene fluoride-co-hexafluoropropylene)/polyaniline (PVDF-co-HFP/PAni) conductive blends were prepared by two methodologies involving the in situ polymerization in two different media and dry blending approach using ball milling. Dodecylbenzenesulfonic acid (DBSA) was used both as surfactant and as protonating agent in PAni synthesis. X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–Vis) spectroscopy, and thermogravimetric analysis were used for characterizing the blends. PAni and PVDF/PAni prepared by in situ polymerization in H₂O/toluene medium exhibited superior electrical conductivity, higher thermal stability and significantly higher electromagnetic interference shielding effectiveness (EMI SE) than those prepared in H₂O/dimethylformamide (DMF) medium. PVDF/PAni with high-PAni content (>40%) prepared by the dry blend approach presented higher conductivity and EMI SE than those prepared by in situ polymerization. The molding temperature exerted significant influence on the conductivity and EMI SE for the blend containing higher amount of PAni. The free-solvent dry blending approach using ball milling presented similar conductivity value but the higher EMI SE when compared with in situ polymerization, and is considered environmentally and technologically interesting.     

Improvement of conductivity of electrochemically synthesized polyaniline

The electrochemical polymerization of aqueous solution of aniline and HCl was carried out in a single compartment electrochemical cell. After 2 h of the polymerization reaction, polarity of the electrodes was reversed and kept for 1 h. By this process the conductivity of the polyaniline (PAni) formed was found to increase dramatically from 1.1 × 10^?4 to 3.0 × 10^?1 S/cm. The PAni samples obtained both by reversing the polarity (“PANI‐R”) and without reversing the polarity (“PANI”) were characterized by the infrared spectroscopy (FT‐IR), thermogravimetric analysis (TGA), ultraviolet spectroscopy (UV), Hall effect experiment, X‐ray analysis (XRD) and scanning electron microscope (SEM). The results show that the increase in the conductivity of PAni through the reversion of polarity is due to the partial reduction of over oxidized sample giving more emeraldine base and hence more polaron formation with increased charge carrier density and its mobility. The degree of crystallinity and the crystallite size is decreased marginally and the d‐spacing is increased marginally due to this reduction. The PAni behaves like a p‐type semiconductor that means the majority current carriers are holes. A plausible reduction mechanism due to reversal of polarity during electrochemical polymerization is also proposed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Polyaniline nanofibers for In situ MAO‐catalyzed polymerization of ethylene

In this work electro‐conductive polyaniline nanofibers (PAni‐nanofibers) were prepared via interfacial methodology. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations revealed that the synthesized PAni‐nanofibers present high aspect ratio with an average diameter of 80 nm, while they exhibit high conductivity (DC conductivity values: 4.19 ± 0.21 S cm^?1). After specific treatment to remove moisture and remaining trapped HCl from PAni‐nanofibers, it was possible to prepare promising polyethylene (PE)/PAni composites by in situ polymerization of ethylene using bis(cyclopentadienyl) zirconium(IV) dichloride (Cp₂ZrCl₂) and methylaluminoxane (MAO) as catalytic system. More precisely, various contents of PAni‐nanofibers (from 0.2 to 7 wt %) were successfully incorporated in the in situ produced PE/PAni nanocomposites. PAni‐nanofibers were found to affect significantly the crystallization of the polyolefinic matrix while preserving its thermal stability. Preliminary measurements of electric properties showed PAni‐nanofibres are able to bring electro‐conductive properties to the in situ polymerized PE/PAni composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41197.     

Electrospun polyaniline nanofibers web electrodes for supercapacitors

Polyaniline nanofibers (PANI‐NFs) web are fabricated by electrospinning and used as electrode materials for supercapacitors. Field‐emission scanning electron microscope micrographs reveal nanofibers web were made up of high aspect ratio (>50) nanofibers of length ～30 μm and average diameter ～200 nm. Their electrochemical performance in aqueous (1M H₂SO₄ and Na₂SO₄) and organic (1M LiClO₄ in propylene carbonate) electrolytes is compared with PANI powder prepared by in situ chemical oxidative polymerization of aniline. The electrochemical properties of PANI‐NFs web and PANI powder are studied using cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. PANI‐NFs web show higher specific capacitance (～267 F g^?1) than chemically synthesized PANI powder (～208 F g^?1) in 1M H₂SO₄. Further, PANI‐NFs web demonstrated very stable and superior performance than its counterpart due to interconnected fibrous morphology facilitating the faster Faradic reaction toward electrolyte and delivered specific capacitance ～230 F g^?1 at 1000th cycle. Capacitance retention of PANI‐NFs web (86%) is higher than that observed for PANI powder (48%) indicating the feasibility of electro spun PANI‐NFs web as superior electrode materials for supercapacitors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of reaction conditions on the formation of nanotubes/nanoparticles of polyaniline in the presence of 1‐amino‐2‐naphthol‐4‐sulfonic acid and applications as electrostatic charge dissipation material

BACKGROUND: Poly(1‐amino‐2‐naphthol‐4‐sulfonic acid) and its copolymers with aniline are a new class of conducting polymers which can acquire intrinsic protonic doping ability, leading to the formation of highly soluble self‐doped homopolymers and copolymers. Free ? OH and ? NH₂ groups in the polymer chain can combine with other functional groups that could be present in protective paints which can thus be successfully used as antistatic materials. RESULTS: This paper reports the formation of nanotubes of polyaniline on carrying out oxidative polymerization of aniline in the presence of 1‐amino‐2‐naphthol‐4‐sulfonic acid (ANSA) in p‐toluenesulfonic acid (PTSA) as an external dopant. The presence of ? SO₃H groups in the ANSA comonomer allows the copolymer to acquire intrinsic protonic doping ability. The polymerization mechanism was investigated by analysing the ¹H NMR, ¹³C NMR, Fourier transform infrared and X‐ray photoelectron spectra of the copolymers and homopolymers, which revealed the involvement of ? OH/? NH₂ in the reaction mechanism. Scanning and transmission electron microscopy showed how the reaction route and the presence of a dopant can affect the morphology and size of the polymers. Static decay time measurements were also carried out on conducting copolymer films prepared by blending of 1 wt% of copolymers of ANSA and aniline with low‐density polyethylene (LDPE) which showed a static decay time of 0.1 to 0.31 s on dissipating a charge from 5000 to 500 V. CONCLUSION: Copolymers of ANSA with aniline were synthesized in different reaction media, leading to the formation of nanotubes and nanoparticles of copolymer. Blends of 1 wt% of PTSA‐ and self‐doped copolymers of ANSA and aniline with LDPE can be formulated into films with effective antistatic properties. Copyright © 2009 Society of Chemical Industry     

Synergistic effect of dopant combination and switchover in formation mechanism of polyaniline nanowire

Self‐assembled polyaniline (PAni) was synthesized electrochemically in dimethylformamide medium to study the effect of simultaneous use of organic–inorganic dopant combination in aprotic polar synthesis medium. During the synthesis process, simultaneous dual doping was performed using p‐toluenesulfonic acid and sulfuric acid with varying the ratio of the dopants keeping their total concentration unchanged. Nanowire meshes were formed where switchover in nanostructure formation is observed. Nanowire in individually doped PAni was formed with directional joining of smaller nanoparticles or from multilayered tubular nanostructures whereas, for dual doped PAni, either of these two was observed. Periodicity parallel and perpendicular to polymer chain were found in well correlation with diameter of nanowires. Synergistic improvements in AC conductivity, specific capacitance, and thermal degradation within certain temperature range were observed in particular ratio of the dopants. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41520.     

Polyaniline salt containing dual dopants,pyrelenediimide tetracarboxylic acid,and sulfuric acid: Fluorescence and supercapacitor

Storage of energy is considered as the most germane technologies to address the future sustainability. In this study, aniline was chemically oxidized with a controlled concentration of pyrelenediimide tetracarboxylic acid (PDITCA) by ammonium persulfate to polyaniline salt (PANI‐H₂SO₄‐PDITCA), with nanorods morphologies, having a sensibly decent conductivity of 0.8 S cm^?1, wherein H₂SO₄ was generated from ammonium persulfate during polymerization. PANI‐H₂SO₄‐PDITCA salt showed bathochromic fluorescence shift (595 nm) compared to PDITCA (546 nm). The Brunauer–Emmett–Teller surface area of the PANI‐H₂SO₄‐PDITCA‐25 and PANI‐H₂SO₄‐PDITCA‐50 were 18.3 and 21.4 m² g^?1, respectively. Furthermore, its energy storage efficiency was evaluated by supercapacitor cell configuration. The composite PANI‐H₂SO₄‐PDITCA‐50 showed capacitance 460 F g^?1 at 0.3 A g^?1 and large cycle life 85,000 cycles with less retention of 77% to its original capacitance (200 F g^?1) even at a better discharge rate of 3.3 A g^?1. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45456.     

Synthesis and characterization of conducting homopolymers and copolymers of o‐anisidine and o‐toluidine in inorganic and organic supporting electrolytes

The influence of inorganic and organic supporting electrolytes on the electrochemical, optical, and conducting properties of poly(o‐anisidine), poly(o‐toluidine), and poly(o‐anisidine‐co‐o‐toluidine) thin films was investigated. Homopolymer and copolymer thin films were synthesized electrochemically, under cyclic voltammetry conditions, in aqueous solutions of inorganic acids (H₂SO₄, HCl, HNO₃, H₃PO₄, and HClO₄) and organic acids (benzoic acid, cinnamic acid, oxalic acid, malonic acid, succinic acid, and adipic acid) at room temperature. The films were characterized by cyclic voltammetry, ultraviolet–visible spectroscopy, and conductivity measurements with a four‐probe technique. The ultraviolet–visible spectra were obtained ex situ in dimethyl sulfoxide. The optical absorption spectra indicated that the formation of the conducting emeraldine salt (ES) phase took place in all the inorganic electrolytes used, whereas in organic acid supporting electrolytes, ES formed only with oxalic acid. Moreover, the current density and conductivity of the thin films was greatly affected by the nature and size of the anion present in the electrolyte. For the copolymer, the conductivity lay between the conductivity of the homopolymers, regardless of the supporting electrolyte used. The formation of the copolymer was also confirmed with differential scanning colorimetry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2634–2642, 2003     

Synthesis of dipropylaniline from aniline and n-propanol

A systematic study has been made of the synthesis of dipropylaniline from aniline and n-propanol using H₂SO₄ and HCl as catalysts. With both catalysts, the optimum temperature, pressure, residence period, mole ratio of aniline to n-propanol and mole ratio of aniline to H⁺ (catalyst) for the synthesis are 245°C, 600 lb/in², 2 h, 1:3 and 1:0.305 respectively. Very high pressure has practically no influence on the reaction and it helps only to form undesirable tarry matter. The maximum conversions of aniline to dipropylaniline under these optimum conditions are 45.53 and 46.57% with H₂SO₄ and HCl respectively. The conversion of aniline to propylaniline is always found to be greater than conversion to dipropylaniline. At the optimum conditions for the synthesis of dipropylaniline, conversions of aniline to propylaniline are 47.75% with H₂SO₄ and 51.55% with HCl.     

Electrochemical synthesis of poly(2‐iodoaniline) and poly(aniline‐co‐2‐iodoaniline) in acetonitrile

Poly(2‐iodoaniline) (PIANI) and poly(aniline‐co‐2‐iodoaniline) [P(An‐co‐2‐IAn)] were synthesized by electrochemical methods in acetonitrile solution containing tetrabutylammonium perchlorate (TBAP) and perchloric acid (HClO₄). The voltametry of the copolymer shows characteristics similar to those of conventional polyaniline (PANI), and it exhibits higher dry electrical conductivity than PIANI and lower than PANI. The observed decrease in the conductivity of the copolymer relative to PANI is attributed to the incorporation of the iodine moieties into the PANI chain. The structure and properties of these conducting films were characterized by FTIR and UV‐Vis spectroscopy and by an electrochemical method (cyclic voltametry). Conductivity values, FTIR and UV‐Vis spectra of the PIANI and copolymer were compared with those of PANI and the relative solubility of the PIANI and the copolymer powders was determined in various organic solvents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1652–1658, 2003     

Electroactive mixtures of polyaniline and EPDM rubber: Chemical,thermal, and morphological characterization

A new route for blending polyaniline (PAni) and EPDM rubber was devised with maleic anhydride as a compatibilizer precursor. Rubber matrices containing ammonium peroxidisulfate and dodecyl benzene sulfonic acid were cast from organic solvents. Exposure to the monomer vapors allowed the chemical polymerization of aniline. The influence of PAni and the compatibilizer on the thermal properties, chemical structure, electrical conductivity, and morphology of the mixtures was observed with differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared, in situ conductivity measurements, and optical microscopy. The micrographs showed a good distribution of the PAni complex in the matrix. The use of approximately 2 wt % compatibilizer resulted in chemical interactions between maleic anhydride and the PAni complex formed with dodecyl benzene sulfonic acid, which could enhance the compatibility between the polymers. The obtained blends reached relative electrical conductivity values of up to 9 × 10^?3 S cm^?1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 535–547, 2003     

Conducting polyaniline‐titanium dioxide nanocomposites prepared by inverted emulsion polymerization

Conducting polyaniline (PAni)‐titanium dioxide (TiO₂) nanocomposites have been synthesized by the inverted emulsion polymerization method. Aqueous mixtures of aniline, a free‐radical oxidant, and/or TiO₂ nanoparticles (∼25 nm in diameter; mixture of anatase and rutile) are utilized to synthesize the hybrid nanocomposites. The polymerization is carried out in an organic solvent (chloroform, CHCl₃) in the presence of a protonic acid (hydrochloric acid, HCl) as a dopant and an emulsifier (cetyl trimethylammonium bromide). The resultant PAni‐TiO₂ nanocomposites are characterized with their structural, morphological, conducting, and optical properties. SEM and TEM images represent the PAni‐TiO₂ nanocomposites with the diameter range of 50–200 nm. Electrical conductivities are checked by standard four‐point probes method and found to be 0.38 S/cm for bulk PAni and 0.11 S/cm for PAni‐TiO₂ nanocomposites. UV–visible absorption shows two electronic bands at about 320 and 596 nm for bulk PAni and the blue‐shifted bands with the intensity changes due to the formation of PAni‐TiO₂ composites. Thermogravimetric analysis reveals that the composites have a higher degradation temperature than the PAni alone. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers