Effect of dopant mixture on the conductivity and thermal stability of polyaniline/nomex conductive fabric

Electrically conductive polyaniline (PANI)/[poly(m‐phenylene isophthalamide)] Nomex composite fabric was prepared by in situ polymerization of aniline doped by a mixture of hydrochloride (HCl) and various sulfonic acids such as benzenesulfonic acid (BSA), sulfosalicylic acid (SSA), and dodecylbenesulfonic acid (DBSA); their effect on conductivity and physical properties were then investigated. PANI/Nomex composite fabrics doped by a mixture of protonic acids exhibited higher conductivity than those doped by other single dopants such as camphorsulfonic acid (CSA), p‐toluenesulfonic acid (TSA), BSA, SSA, and HCl. The conductivity of PANI/Nomex fabrics especially doped by a mixture of HCl and DBSA was evenly maintained up to 100°C without depression of mechanical properties of Nomex. Their conductivity was also maintained under extension of the composite fabric. In addition, electrical conductivity of PANI/Nomex fabrics was highly increased by ultrasonic treatment, which facilitated better diffusion and adsorption of aniline by cavitation and vibration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2245–2254, 2002     

Electrical,physicomechanical, and X‐ray studies on ethylene‐vinyl acetate copolymer/polyaniline blends

The conductive blend consisting of ethylene‐vinyl acetate (EVA) and a polyaniline/p‐toluene sulfonic acid (PAn/TSA) complex were prepared by a thermal doping process using a Brabender plasticorder at 150°C. The conductivity, dielectric constant, dissipation factor, mechanical behavior, and structural aspects of these blends were investigated. A higher percentage of the PAn/TSA complex in the EVA matrix resulted in an increase in the electrical properties and a decrease in the mechanical properties like the tensile strength and percentage of elongation. These results were compared with the microcrystalline parameters of the blend obtained from X‐ray profile analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1730–1735, 2002     

Properties evaluation of the membranes synthesized with castor oil polyurethane and polyaniline

Polymeric membranes for electrodialysis, fuel cells, and other purposes with specific characteristics have been the focus of innumerable researches. The aim of this work was to evaluate membranes of the sulfonated polyaniline and polyurethane, obtained in the presence of the former, regarding its mechanical and electrical properties. Polyurethane (PU) was prepared from castor oil and 4–4‐diciclohexilmethane isocyanate (HMDI). Polyaniline was synthesized by chemical oxidation, as described in the literature, and was sulfonated with chlorosulfonic acid in dichloroethane. Solution membranes were prepared by mixing sulfonated polyaniline (SPAN) and polyaniline doped with p‐toluene sulfonic acid (PAni_TSA) with castor oil and further HMDI. The obtained products were characterized by FTIR, TGA, and DMA. The membrane FTIR brought out the characteristic peaks of PU and polyanilines (TSA e sulfonated), and TGA curve showed a maximum decomposition rate at 350°C, quite different of the polyaniline ones. Nevertheless the SPAN/PU membrane showed very good stability until 250°C. The loss modulus curves show that there was an increase in the PU glass transition temperature with the addition of PAni and SPAN due to the their interaction with the PU chains. POLYM. ENG. SCI. 46:1485–1489, 2006. © 2006 Society of Plastics Engineers.     

Surface graft polymerization of conducting polyaniline on waterborne poyurethane‐urea film and its phenol sensing

Waterborne polyurethane‐ureas (pristine WBPUs: WBPU‐19 and WBPU‐24, fixed soft segment content: 60 wt %) containing dimethylol propionic acid (DMPA)/ethylene diamine (EDA) contents (19/16.8 and 24/11.4 mol %) were prepared. The polyaniline (PANI)‐graft‐WBPU (PANI‐graft‐WBPU) films were prepared by oxidative graft polymerization of aniline on the surface layer of WBPU films. This study focused on the effects of reaction conditions (concentrations/treating times/temperatures of aniline and APS) and DMPA content on the %grafting, conductivity, and mechanical properties of PANI‐graft‐WBPU films. To obtain the maximum %grafting (PANI‐graft‐WBPU‐19: 6.2, and PANI‐graft‐WBPU‐24: 7.4) and conductivity (PANI‐graft‐WBPU‐19: 3.6 × 10^?2S/cm, and PANI‐graft‐WBPU‐24: 4.7 × 10^?2S/cm), the optimum concentrations/treating times/temperatures of aniline and APS, were found to be 0.35M/10 min/25°C and 0.2M/10 min/0°C, respectively. The tensile strength of film samples was found to be increased in the order of PANI‐graft‐WBPU‐19>pristine WBPU‐19>PANI‐graft‐WBPU‐24>pristine WBPU‐24. The PANI‐graft‐WBPU‐19 (%grafting: 6.2) films on exposure to 0–10,000 ppm phenol solutions showed a well‐defined response behavior, demonstrating high promise for application in aqueous phenol sensors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Water‐dispersible conducting polyaniline/nano‐SiO2 composites without any stabilizer

A water‐dispersible conducting polyaniline/ nano‐SiO₂ composite, with a conductivity of 0.071 S cm^?1 at 25°C, was prepared by the oxidative polymerization of aniline in the presence of amorphous nano‐SiO₂ particles. And the structure, morphology, thermal stability, conductivity, and electroactivity of this composite were also investigated. This composite has been steadily dispersed in the aqueous solution for about 10–36 h without the need for any stabilizer. It would significantly impulse the commercial applications of conducting polyaniline/nano‐SiO₂ composite as fillers for antistatic and anticorrosion coatings. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanism of formation of polyaniline flakes with high degree of crystallization using a soft template in the presence of cetyltrimethy‐lammonium bromide

Flake‐like polyaniline with various thicknesses was prepared by cationic emulsion polymerization of aniline monomer in the presence of cetyltrimethylammonium bromide (CTAB). The morphology of polyaniline with uniform and smooth flake‐like structure was observed using field‐emission scanning electron microscopy and transmission electron microscopy. The lamellar complex of (CTA)₂S₂O₈, acting as a reactive soft template for the formation of polyaniline, was investigated using low‐angle X‐ray diffraction. The soft template provides an expanding space for the growth of polyaniline, in which the oxidization of aniline monomers can construct effectively a flake‐like structure. The concentration of CTAB plays an important role in adjusting the d‐spacing of the soft template. Crystallization and composition of polyaniline were characterized using X‐ray diffraction and Fourier transform infrared spectroscopy. The X‐ray diffraction pattern has a sharp peak at 2θ = 6.4° (d‐spacing = 13.7 Å), showing that polyaniline has a solid‐state ordering structure and high degree of crystallization. Doping and dispersive experiments were also included in the study. Copyright © 2012 Society of Chemical Industry     

Morphology controlled synthesis of polyaniline nanostructures using swollen liquid crystal templates

Preparation of zero‐dimensional and one‐dimensional nanostructures of polyaniline (PANI) were achieved by using swollen liquid crystals (SLCs) as ‘soft' templates. The monomer (aniline) was first entrapped in SLCs by replacing the oil phase (cyclohexane) with a mixture of aniline and cyclohexane. Zero‐dimensional nanostructures of PANI were obtained by thorough mixing of APS with the mesophases. One‐dimensional nanostructures were prepared by allowing slow diffusion of APS through the mesophase. PANI nanostructures were extracted from the mesophase and were characterized by UV‐visible spectroscopy, FTIR spectroscopy, powder X‐ray diffraction, atomic force microscopy, scanning electron microscopy (SEM), and conductivity measurements. A plausible mechanism for the formation of the nanostructures has been proposed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40800.     

Stability of polyaniline synthesized by a doping–dedoping–redoping method

Stability, including thermal stability, conductivity stability in air and after thermal treatment (100–200°C), of the polyaniline (PANI) films synthesized by a doping–dedoping–redoping method was investigated. It was found that thermogravimetric analysis (TGA) curves undergo three steps: loss of water or solvent, dedoping and decomposition, and those depend on the counterions. Compared with PANI films doped with camphor sulfonic acid (CSA) in m‐cresol, the thermal stability of the doped PANI films is improved by the new method, and thermal stability in the order of PANI–H₃PO₄ > PANI–p‐TSA > PANI–H₂SO₄ > PANI–HCl, PANI–HClO₄ > PANI–CSA was observed. The conductivity of the doped PANI films at room temperature was reduced after thermal treatment, and it is dependent of the counterions. It was found that the conductivity stability of PANI–p‐TSA and PANI–CSA is the best below 200°C. When the doped PANI films were placed in air, their conductivity decrease slowly with time due to deproton, and also depends on the counterions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 615–621, 1999     

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

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

Effect of dopant type on the properties of polyaniline

The comparative study on the effect of different type of dopants on the properties of polyaniline (PANI) is relative less although dopant has profound effect of the properties of PANI. So, the aim of the present work is to study the effect of different type of dopant, namely strong inorganic hydrochloric acid (HCl), organic and aromatic acids containing different aromatic substitution, namely p‐toluene sulfonic acid (PTSA), dodecylbenzenesulfonic acid (DBSA), organic and aliphatic acids having long hydrocarbon chain, namely lauric acid (LA), on the properties of PANI. The PANI was prepared through oxidative polymerization methods and doped with HCl, PTSA, DBSA, and LA and then characterized through different methods like conductivity measurement, UV, X‐ray, DSC, TGA, and SEM. It was found that the properties of doped PANI depend on the type and molecular size of the dopant. With the increase in dopant chain length, the crystallinity is decreased, whereas the d‐spacing, interchain separation, and solubility are increased. The bond formation of water molecules with the backbone nitrogen of the polymers is much less in presence of aromatic dopants when compared with those of inorganic or aliphatic dopants. All the doped polyanilines under investigation do not decompose up to 500°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polyaniline encapsulated microporous polymer beads and their vapor and gas adsorption behavior

Styrene‐maleic acid copolymer beads and styrene‐divinylbenzene beads were encapsulated with polyaniline by insitu oxidative polymerization of aniline. These beads both in unmodified and encapsulated forms were studied for their organic vapor and hydrogen adsorption behavior at 30°C and reduced pressure. Enhanced adsorption of hydrogen to the extent of 4.9 mass % was observed for encapsulated styrene‐maleic acid copolymer beads. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 297–303, 2007     

Synthesis and physicochemical properties of poly[2‐(2‐chloro‐1‐methylbut‐2‐en‐1‐yl)aniline] obtained with various dopants

Highly soluble polyaniline was synthesized from a newly designed aniline derivative, namely 2‐[2‐chloro‐1‐methylbut‐2‐en‐1‐yl]aniline. The corresponding polyanilines, PClPA‐HA, PClPA‐SA, PClPA‐NA and PClPA‐PA, were characterized by means of ¹H NMR, ¹³C NMR, high resolution mass spectroscopy, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy and SEM images. The elemental analysis and electrical conductivity of the polymers are also presented. It is shown that the molecular weight of the polymers obtained depends on the method of synthesis. Spectroscopic studies confirmed the emeraldine form of the polyaniline derivatives. In the work, the dependence of the current passing through resistive structures based on thin poly[2‐(2‐chloro‐1‐methylbut‐2‐en‐1‐yl)aniline] films on the relative humidity of air was studied. The results of the studies showed the prospects of using thin polymer films in the design of chemical sensors. © 2020 Society of Chemical Industry     

Synthesis of conducting polyaniline/TiO2 composite nanofibres by one‐step in situ polymerization method

Conducting polyaniline (PANI)/titanium dioxide (TiO₂) composite nanofibres with an average diameter of 80–100 nm were prepared by one‐step in situ polymerization method in the presence of anatase nano‐TiO₂ particles, and were characterized via Fourier‐transform infrared spectra, UV/vis spectra, wide‐angle X‐ray diffraction, thermogravimetric analysis, and transmission electron microscopy, as well as conductivity and cyclic voltammetry. The formation mechanism of PANI/TiO₂ composite nanofibres was also discussed. This composite contained ～ 65% conducting PANI by mass, with a conductivity of 1.42 S cm^?1 at 25°C, and the conductivity of control PANI was 2.4 S cm^?1 at 25°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Optimization of preparation conditions on the dielectric properties of polyaniline

The dielectric response in the microwave field of polyaniline prepared at different temperatures and using different inorganic and organic dopants was studied. Chemical oxidative polymerization of aniline was done at low temperature (0–5°C), at room temperature, and at high (60°C) temperature using different inorganic dopants like HCl, HNO₃, H₂SO₄, HClO₄, etc. Polyaniline was also prepared with different organic dopants like camphor sulfonic acid, Toluene sulfonic acid, and Naphthalene sulfonic acid. All polymers formed were characterized using IR, TGA, DSC, and SEM, etc. The dielectric responses of all polymers are studied using cavity perturbation technique in the microwave field. The studies indicates that the polyaniline prepared with perchloric acid at room temperature shows higher conductivity and absorption coefficient compared with all other samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Catalytic-assisted synthesis, characterization and low frequency AC conduction of nanostructured conducting polyaniline

Polymerizations of aniline at the reaction temperatures of 25 and 50 °C have been performed in the presence of iron catalyst. The prepared conducting polyaniline at different reaction periods was investigated for physicochemical and electrical properties, through X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–Visible spectroscopy (UV–Vis), Fourier transform infrared spectroscopy (FTIR) and frequency-dependent electrical conductivity measurements, respectively. XRD studies established the improved nanostructured crystalline nature for the polymer prepared at 50 °C. Size of the particles ranging from 10 to 20 nm was calculated for the prepared polyaniline. SEM analysis shows the cauliflower-like morphology for optimized reaction temperature. The study further establishes the attainment of uniform distribution of polyaniline at the reaction temperature of 50 °C. The charge transitions between benzenoid (B-band) and quinonoid (Q-band) bands were witnessed by UV–Vis spectrum analysis. The band gap analysis revealed the narrow band gap direct transition semiconducting nature of the conducting polymer. Quinonoid and phenylene rings were identified through vibrational bands between 1570 and 827 cm^?1 via FTIR spectroscopy analysis. The AC conductivity of the sample synthesized at 50 °C showed 1.50 × 10^?1 S cm^?1. Enhancement in conductivity with increasing temperature represented the improved crystalline nature of the polyaniline prepared at 50 °C.     

A novel soluble PANI/TPU composite doped with inorganic and organic compound acid

A series of novel soluble and thermoplastic polyurethane/polyaniline (TPU/PANI) composites doped with a compound acid, which was composed of an organic acid (p‐toluene sulfonic acid) and an inorganic acid (phosphoric acid), were successfully prepared by in situ polymerization. The effect of aniline (ANI) content, ratio of organic acid/inorganic acid, and different preparation methods on the conductivity of the TPU/PANI composites were investigated by using conductivity measurement. Lithium bisoxalato borate (LiBOB) was added to the prepared in situ TPU/PANI to coordinate with the ether oxygen groups originating from the soft molecular chains of TPU, and thus the conductivity of the composites was further enhanced. The molecular structure, thermal properties, and morphology of the TPU/PANI composites were studied by UV–visible spectroscopy, differential scanning calorimetry, and scanning electron microscopy, respectively. The results show that the in situ TPU/PANI composites doped with the compound acid can be easily dissolved in normal solvents such as dimethylformamide (DMF) and 1,4‐dioxane. The conductivity of the TPU/PANI composites increases with the increase of the ANI content, in the ANI content range of 0–20 wt %; however, the conductivity of the composites reduces with further increment of ANI content. The conductivity of the TPU/PANI composites prepared by in situ polymerization is about two orders of magnitude higher than that prepared by solution blending method. LiBOB can endow the in situ TPU/PANI composites with an ionic conductivity. The dependence of the conductivity on temperature is in good accordance with the Arrhenius equation in the temperature range of 20–80°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel oxidants for polymerization and crystallization of aniline

By using novel oxidants, namely, sodium salt of para‐toluene sulfonic acid, lithium perchlorate, and potassium ferricyanide, and varying the oxidant to monomer ratio from as low as 1/100 to 1/20 in the presence of concentrated HCl, it has been possible to simultaneously polymerize aniline and crystallize the polyaniline at room temperature. The crystals thus obtained have been characterized using FTIR, GPC, XRD, and Optical Microscope. It was found that highly crystalline substituted oligo‐polyanilines were obtained. The studies indicate that the use of even weaker oxidants, like pTS‐Na, LiClO₄, and K₃[Fe(CN)₆], can bring about simultaneous polymerization and crystallization of aniline, as we observed earlier using ammonium persulphate. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 640–646, 2005     

Copolymerization of poly(1‐naphthylamine) with aniline and o‐toluidine

The commercial use of polyaniline has been impeded by its intractable nature and insolubility. The use of substituted polyaniline has been attempted mainly to increase the processibility of polyaniline, but this approach usually results in the lowering of the conductivity. This study reports the synthesis of poly(1‐naphthylamine), a fused ring derivative of polyaniline, and its copolymers with aniline and o‐toluidine via a chemical polymerization method. Spectral, thermal, morphological, and conductivity studies were carried out to elucidate the influence of the incorporation of aniline and o‐toluidine units into poly(1‐naphthylamine). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrical conductivity and electromagnetic interference shielding of polyaniline/polyacrylate composite coatings

Lightweight and flexible composite coatings of p‐toluene sulfonic acid doped polyaniline (PANI–TSA) with various mass fractions and polyacrylate were prepared for electromagnetic interference (EMI) shielding. Both the volume and surface conductivities of the composite coatings increased with increasing PANI–TSA; furthermore, the volume conductivity showed a typical percolation behavior with a percolation threshold at about 0.21. The EMI shielding effectiveness (SE) of the PANI–TSA/polyacrylate coatings over the range of 14 kHz to 15 GHz increased with increasing PANI–TSA as the direct‐current conductivity did. EMI SE of the coatings at the low frequencies (14 kHz to 1 GHz) was around 30–80 dB, higher than that at the high frequencies (1–15 GHz); this indicated possible commercial application of the coatings for far‐field EMI shielding. The highest EMI SE value was 79 dB at 200 MHz with a coating thickness of 70 ± 5 μm. The moderate SE, light weight, and easy preparation of the coating are advantages for future applications for EMI shielding. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2149–2156, 2005     

A conducting composite based on poly(N‐vinylcarbazole)–formalin resin and acetylene black

A poly(N‐vinylcarbazole) (PNVC)–formalin (FO) resin (PNVC‐FO) was prepared via copolycondensation between N‐vinylcarbazole (NVC) and FO in the presence of dry HCl gas in toluene medium at 110°C. A highly conducting composite of PNVC‐FO resin with nanodimensional acetylene black (AB) was prepared by carrying out the polycondensation reaction in presence of a suspension of acetylene black (AB) in toluene. The inclusion of PNVC in the PNVC‐FO‐AB composite was confirmed by FT‐IR analysis. Scanning electron microscopic analyses of PNVC‐FO resin and PNVC‐FO‐AB composite revealed formation of spherical particles and aggregates of irregular shapes respectively. Thermogravimetric analyses revealed the overall stability order as: AB > PNVC‐FO‐AB composite > PNVC‐FO resin > PNVC homopolymer. In sharp contrast to PNVC and PNVC‐FO resin, which were both nonconducting (10^?12 to 10^?16 S/cm), the conductivity of the composites reached values between 0.75 S/cm and 6.54 S/cm corresponding to AB loading of 28–49 wt % respectively. Temperature versus conductivity studies revealed an initial increase in conductivity upto 200°C and current–voltage characteristics of the PNVC‐FO‐AB composite showed a linear trend consistent with Ohmic behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3837–3843, 2007