Doped polyaniline/multiwalled carbon nanotube composites: Preparation and characterization

Polyaniline (PANI)/multiwalled carbon nanotube (MWNT) composites with a uniform tubular structure were prepared from in situ polymerization by dissolving amino‐functionalized MWNT (a‐MWNT) in aniline monomer. For this the oxidized multiwalled nanotube was functionalized with ethylenediamine, which provided ethylenediamine functional group on the MWNT surface confirmed by Fourier‐transform infrared spectra (FT‐IR). The a‐MWNT was dissolved in aniline monomer, and the in situ polymerization of aniline in the presence of these well dispersed nanotubes yielded a novel tubular composite of carbon nanotube having an ordered uniform encapsulation of doped polyaniline. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the nanotubes were coated with a PANI layer. The thermal stability and electrical conductivity of the PANI /MWNTs composites were characterized by thermogravimetric analysis (TGA) and conventional four‐probe method respectively. Compared with pure PANI, the electrical conductivity and the decomposition temperature of the MWNTs/PANI composites increased with the enhancement of MWNT content in PANI matrix. POLYM. COMPOS., 34:1119–1125, 2013. © 2013 Society of Plastics Engineers     

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     

Water‐dispersible nanocomposites of polyaniline and montmorillonite

The polymerization of aniline (ANI) in aqueous medium in the presence of (NH₄)₂S₂O₈ and montmorillonite (MMT) resulted in the formation of a nanocomposite (PANI–MMT). The inclusion of PANI in the composite was confirmed by FTIR studies. The extent of PANI loading in the composite increased with ANI concentration at a fixed oxidant/MMT amount and with the oxidant amount at a fixed ANI and MMT weight, but decreased with an MMT amount at a fixed ANI and oxidant level. TGA revealed a higher stability for the PANI–MMT composite relative to PANI and confirmed a PANI loading of ca. 51% in the composite. The conductivity increased in all the cases. XRD analysis revealed no expansion of the d₀₀₁ spacing at 9.8 Å, implying no intercalation of PANI within the MMT layers. Scanning electron micrography studies revealed interesting morphological features for the composites. Transmission electron micrography analysis revealed distinctive features and confirmed the formation of PANI–MMT composite particles of diameters in the 300‐ to 400‐nm range. These composites could be obtained as stable colloids in the presence of poly (N‐vinyl pyrrolidone) under selective conditions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2948–2956, 2000     

Nanocomposite of polyaniline and a layered niobate acid host: Synthesis,electrochemical studies,and photocatalytic properties

The synthesis of polyaniline (PANI) with H₄Nb₆O₁₇ (HNbO) to form PANI/HNbO lamellar nanocomposite by in situ polymerization using aniline (ANI) intercalation compound ANI/HNbO as the intermediate has been investigated. The properties of the samples were characterized by means of XRD, SEM, TEM, FT‐IR, UV–vis spectroscopy, and TG‐DTA. The in situ polymerization of ANI packed in a regular orientation in a mono‐ and bilayers (i.e., pseudo‐bilayers) structure within the HNbO interlayers led to PANI/HNbO nanocomposite powder using (NH₄)₂S₂O₈ as the catalyst with PANI monolayer packing orientation within the HNbO interlayers. PANI/HNbO nanocomposite showed improved thermal stability compared with original PANI by TG analysis. The PANI/HNbO nanocomposite was studied by cyclic voltammetry (CV), which indicated the good redox activity and electrochemical‐cycling stability in acidic solution. The interaction between PANI and nanosheets greatly affected the electrochemical behavior of PANI/HNbO nanocomposite. Two couples of redox peaks corresponded to two oxidation process of PANI in acid conditions. The PANI/HNbO nanocomposite exhibited much higher photocatalytic activities for the degradation of methylene blue (MB) in aqueous solution under visible light irradiation than HNbO itself. POLYM. COMPOS., 34:834–841, 2013. © 2013 Society of Plastics Engineers     

Melt/solution processable polyaniline with functionalized phosphate ester dopants and its thermoplastic blends

Polyaniline (PANI) was doped with five novel dopants, 3‐pentadecylphenylphosphoric acid (PDPPA), pentadecylphenyl(bis)phosphoric acid [PDP(bis)PA], monocardanylphosphoric acid (MCPA), dicardanylphosphoric acid (DCPA), and phosphorylated cashew nut shell liquid prepolymer (PCNSL) and the doping behavior was studied. All dopants were synthesized from inexpensive naturally existing monomers [obtained from cashew nut shell liquid (CNSL)] having a long hydrophobic hydrocarbon side chain in the meta position of the aromatic ring. These dopants can act as plasticizing cum protonating agents for PANI so that free‐standing films of PANI could be prepared by both thermal processing and solution processing techniques. Protonation was performed either by mechanical mixing of emeraldine base and the dopant or by an in situ doping emulsion polymerization route using xylene or chloroform as the solvent. Further, conductive flexible blends of the protonated PANI with poly(vinyl chloride) (PVC) were also prepared and studied for their conductivity and related properties. The PANI–PDPPA complex obtained by the in situ doping emulsion polymerization route exhibited an exceptionally high degree of crystalline order and orientation. A maximum conductivity value of 1.8 S cm^?1 was obtained for a PANI–PDPPA film hot‐pressed at 120°C. On the other hand, dopants based on cardanol having an unsaturated side chain gave only lower values. This was understood to be due the capability of the saturated analog to contribute to the ordered arrangement of PANI, thus improving the crystallinity. The conductivity values further decreased when bulky/oligomeric dopants such as PCNSL were used. The thermoplastic blends with PVC exhibited an exceptionally low‐level percolation threshold because of the plasticizing nature of the dopants. The doped polymers and blends were characterized by FTIR and UV‐visible spectroscopic methods, four‐probe conductivity measurements, XRD, SEM, TGA, and DSC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1354–1367, 2001     

Preparation and characterization of composites of polyaniline nanorods and multiwalled carbon nanotubes coated with polyaniline

Composites of polyaniline (PANI) nanorods and multiwalled carbon nanotubes (MWNTs) coated with PANI were prepared by in situ polymerization with perchloric acid as a dopant. Transmission electron microscopy images showed that the coexisting composites of PANI nanorods and MWNTs coated with PANI were formed at low MWNT contents. The interaction between MWNTs and PANI was proved by Fourier transform infrared and ultraviolet–visible spectra. The electrical conductivity of a dedoped PANI/MWNT composite with a 16.3 wt % concentration of MWNTs reached 3.0 × 10^?3 S/cm, which was 6 orders of magnitude higher than that of dedoped PANInanorods. The results also showed that coexisting composites of PANI nanorods and MWNTs coated with PANI had high electrochemical activity and good cyclic stability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Polyaniline-Coated Short Nylon Fiber/Natural Rubber Conducting Composite

Natural rubber-Polyaniline (PANI)-Polyaniline coated short nylon-6 fiber (PANI-N6) composites were prepared by mechanical mixing and its cure characteristics, filler dispersion, mechanical properties, conductivity and thermal stability were evaluated. PANI was synthesized by chemical oxidative polymerization of aniline in presence of hydrochloric acid. PANI-N6 was prepared by in situ polymerization of aniline in the presence of short nylon-6 fiber. The composite showed higher tensile strength, tear strength and modulus values and lower elongation at break. The DC electrical conductivity and the thermal stability of the composites increased with PANI and PANI-N6 concentration. The highest conductivity obtained was 1.99 × 10^?6 S/cm.     

Electrically conductive carbon nanopipe-graphite nanosheet/polyaniline composites

Carbon nanopipe (CNP)–graphite nanosheet (GNS)/polyaniline (PANI) composites are synthesized by in situ chemical oxidative polymerization. The structural analysis (electron microscopy, Raman and X-ray diffraction) reveal that PANI is uniformly coated on both CNP and GNS structures resulting in the formation of a network of uniform composite structures. Thermogravimetric analysis shows that CNP–GNS/PANI composites are thermally stable up to 300 °C; the polymeric backbone degrades above 300 °C. CNP–GNS/PANI composites doped with m-cresol, a mixture of camphor sulfonic acid (CSA) and chloroform, and a mixture of CSA and m-cresol are electrically conductive. The electrical conductivity strongly depends on the dopants and about six orders of variation in conductivity can be achieved through the choice of the dopant.     

Effect of dopant and oxidant on the electrochemical properties of polyaniline/graphite nanoplate composites

Optimizing the synthesis parameters of polyaniline/graphite nanoplate (PANI/GNP) composite is essential to the final electrochemical performance. Herein, the electrochemical properties of PANI/GNP composites, prepared by in situ chemical polymerization using varying amounts of different oxidants, with or without the addition of 4‐dodecylbenzenesulfonic acid (DBSA) as dopant, were investigated. Cyclic voltammetric results suggested that a stoichiometric amount of the oxidant iron chloride (FeCl₃) was beneficial to the electrochemical properties of the composites. The use of ammonium persulfate (APS) instead of FeCl₃ as oxidant largely increased the actual PANI content, conductivity and specific capacitance of the PANI/GNP composites. The dopant DBSA increased the conductivity of the PANI/GNP composites but did not show a positive effect on the electrochemical behavior. The cyclic voltammograms of the PANI/GNP composites indicated that the pseudocapacitance of PANI contributes more than the electrical double‐layer capacitance of GNP to the capacitance of the composites, while the presence of GNP plays an essential role in the rate capability of the composites. In this study, PANI/GNP (1:1) composite synthesized with an APS to aniline molar ratio of 1 showed a balanced combination of high specific capacitance (180.5 F g^?1 at 20 mV s^?1) and good rate capability (78% retention at 100 mV s^?1). © 2018 Society of Chemical Industry     

Preparation and characterization of polyaniline–polypyrrole composite from polyaniline dispersions

Polyaniline–polypyrrole (PANI‐PPy) composite was prepared by in situ polymerization of pyrrole in PANI dispersion using FeCl₃·6H₂O as oxidant and sodium dodecyl benzene sulfonate (SDBS) as surfactant. Different synthesis conditions of PANI dispersion including the relative concentration of aniline and SDBS and the amount of acid (HCl) on the morphology and conductivity of the resulting composites were investigated. Fourier transformation infrared (FTIR) spectra, X‐ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), X‐ray diffraction (XRD) patterns, and contact angles of the composites showed there existed certain interaction between PANI (or PANI‐SDBS) and PPy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3523–3529, 2007     

PANI–LDPE composites: Effect of blending conditions

A composite based on polyaniline (PANI) and low density polyethylene (LDPE) with electrical conductivity was developed. Polyaniline was polymerized by chemical oxidation and doped with dodecyl‐benzene‐sulfonic acid (DBSA). PANI–LDPE composites were prepared via melt blending and the films were obtained by compression molding. The influence of three variables of the blending (temperature, [PANI], rotor speed) on conductivity, microstructure and mechanical properties of the composites was studied by means of statistical tools and a 2³ experimental design. The results show that the PANI concentration is the most influential variable, which mainly affects the conductivity and the elongation at break of the composites. These changes are related to the microstructure of the composites. Statistically, the other variables don't show significant influence on conductivity and mechanical properties in the studied range. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

Doping effects of cerium ion on structure and electrochemical properties of polyaniline

Polyaniline (PANI)/Ce³⁺ and PANI/Ce⁴⁺ composites were successfully prepared by in situ polymerization in an aqueous solution of poly(2‐acrylamido‐2‐methylpropane sulfonic acid) and characterized by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, X‐ray photoelectron spectroscopy, SEM, TEM and electrochemical methods. The results showed that the PANI/Ce ion composites had a high degree of sphericity, high electrical conductivity and good electrochemical performance. The conductivity of PANI/Ce(NO₃)₃ reaches a maximum of 46.76 S cm^?1 at 20 wt% of Ce(NO₃)₃. It is increased by 377% by comparison with that of pure PANI. In particular, the polarization results showed that the corrosion current density (0.47 µA cm^?2) and the inhibition efficiency (97%) of PANI/Ce(NO₃)₃ were better than the results for PANI and PANI/Ce(SO₄)₂ composite. This suggested that the PANI/Ce(NO₃)₃ composite has promising applications in conductive materials, anticorrosion coatings and other related fields. © 2017 Society of Chemical Industry     

Studies on SLS doped polyaniline and its blend with PC

Electrically conductive polyaniline (PANI) and its blend with polycarbonate (PC) was prepared by one-step emulsion polymerization technique in which sodium lauryl sulfate (SLS) acts as surfactant and as a protonating agent for the resulting polymer. The prepared PANI and its blends were characterized by density, percentage of water absorption, and electrical conductivity. PANI–PC blend exhibits a conductivity value of 4.70 × 10⁻² S/cm (PANI–PC1) and 5.68 × 10⁻⁵ S/cm (PANI–PC3) with a change in dopant from p-toluene sulfonic acid (TSA) to SLS, respectively. By using a more general method, which takes into account the presence of disorder of the second kind in polymers proposed by Hosemann, crystal size (〈N〉) and lattice strain (g in %) values were estimated. The variation of conductivity in doped PANI and PANI–PC blend has been explained on the basis of these microcrystalline parameters. TGA thermograms of PANI and PANI-PC blend show three-step degradation behavior. Thermal stability of PANI was improved after blending with PC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 383–388, 2001     

Comparison between different conditions of the chemical polymerization of polyaniline on top of PET films

Composites produced during the in situ chemical polymerization of aniline on top of a poly(ethylene terephthalate) (PET) film, in different conditions, were studied by open‐circuit potential (Voc), ultraviolet‐visible, and infrared spectroscopy, electrical conductivity measurements, scanning electron microscopy, and atomic force microscopy. The polymerization monitoring by Voc showed a maximum associated with the intermediate pernigraniline oxidation state and a final formation of polyaniline (PANI) in the doped emeraldine salt (ES) form. Furthermore, high electrical conductivity values were obtained for the PANI–ES coating prepared under selected conditions. A globular formation was observed for the doped PANI–ES coating with globules of sizes of the same order and same shape of the PET, demonstrating the influence of the substrate on the coating morphology. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1220–1229, 2001     

Morphology and electric conductivity controlling of in situ polymerized poly(decamethylene dodecanoamide)/polyaniline composites

In situ polymerization was proved to be an effective method to prepare composites with combined properties of two intrinsic different components. In this study, poly(decamethylene dodecanoamide) (polyamide 1012, PA1012) powders with controlled morphologies and crystal forms were obtained by antisolvent precipitation, whose morphology and crystal forms were strongly dependent on the types and temperatures of antisolvents. PA1012/polyaniline (PA1012/PANI) composites with different morphologies were manufactured through in situ polymerization. Fourier transform infrared spectroscopy results revealed a strong interaction between PA1012 and PANI components. PANI components were in situ polymerized from aniline monomers on the surface of PA1012 powders, forming a composite aggregates in solution. The conductivity of different PA1012/PANI composite powders was about 10⁻⁵–10⁻³ S/cm, which could successfully meet the requirement of antistatic coating. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47041.     

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     

Studies of AC conductivity and dielectric relaxation behavior of CdO‐doped nanometric polyaniline

The Cadmium oxide doped in nanocrystalline polyaniline (CdO/PANI) composite were prepared with various weight percentages by in situ polymerization method using aniline, ammonium per sulfate, and CdO as starting materials. The frequency dependent conductivity and dielectric behavior of PANI/CdO composites have been studied. The formation of nano PANI and PANI/CdO composites with regards to the structural and microstructural properties of the materials were investigated by XRD, FTIR, and SEM techniques. The variation of σ_ac with frequency obeys Jonscher power law except a small deviation in the low frequency region and is due to dipole polarization effect. The σ_ac increases with increase in CdO concentration. Studies of dielectric properties at lower frequencies show that the relaxation behavior is superimposed by dipole polarization effect. The appearance of peak for each concentration in the loss tangent suggests the presence of relaxing dipoles in the PANI/CdO composite. On addition of CdO, the peak shifts toward higher frequency side indicating the speed up of the relaxation time. Analysis of frequency dependent dielectric suggests that the electronic and polymer segmental motions are strongly coupled. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Molecular composites obtained by polyaniline synthesis in the presence of p‐octasulfonated calixarene macrocycle

Polyaniline (PANI) molecular composites were synthesized by chemical oxidative polymerization of the aniline and aniline dimer, N‐phenyl‐1,4‐phenylendiamine, in the presence of a macrocycle, calix[8]arene p‐octasulfonic acid (C8S), using ammonium peroxidisulfate as oxidant. The macrocycle has acted both as acid dopant and surfactant to obtain processable PANI‐ES. The PANI/calix[8]arene p‐octasulfonic acid composite was also obtained by a simple doping of PANI emeraldine base form with calix[8]arene sulfonic acid. The structure of materials was confirmed by Fourier transform infrared, UV–vis and nuclear magnetic resonance spectroscopy. All synthesized composite materials are amorphous and soluble in chloroform, dimethylsulfoxide, NMP, showing excellent solution‐processing properties combined with electrical conductivity. Cyclic voltammetry evidenced a good electroactivity for the composite films. Dielectric properties (dielectric constant and dielectric losses) were determined and are comparable with those of other PANI/ionic acid polymer composites. Preliminary studies have evidenced a high dielectric constant (10⁴ at 100 Hz) and electrical conductivity of 6 × 10^?3 S/cm for PANI composites. From sulfur elemental analysis of the PANI/calixarene, it results that the content in macrocycle is ～30% (weight). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrical and structural analysis of conductive polyaniline/polyimide blends

Conducting films of dodecylbenzenesulfonic (DBSA)‐doped polyaniline/polyimide (PANI/PI) blends with various compositions were prepared by solvent casting followed by a thermal imidization process. Electrical and physical properties of the blends were characterized by infrared spectroscopy, an X‐ray diffraction technique, thermal analysis, a UV‐vis spectrophotometer, a dielectrometer, and conductivity measurements. The blends exhibited a relatively low percolation threshold of electrical conductivity at 5 wt % PANI content and showed higher conductivity than that of pure DBSA‐doped PANI when the PANI content exceeded 20 wt %. A lower percolation threshold and a lower compatibility was shown between the two components in the blends than those of PANI–camphorsulfonic acid/polyamic acid (PANI–CSA/PAA). A well‐defined layered structure due to the alignment of the long alkyl chain dopant perpendicular to the PANI main chain was evidenced by WAXD spectra. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2169–2178, 1999     

Fabrication of honeycomb‐patterned polyaniline composite films containing cellulose triacetate with high conductivity and mechanical stability

Polyaniline (PANI) biocomposites were prepared via in situ polymerization of aniline monomer with cellulose triacetate (CTA) and by using ammonium persulfate as an initiator in an aqueous solvent. The composites exhibited high solubility in organic solvents due to the incorporated CTA component, and enabled the fabrication of honeycomb‐patterned thin films by casting the PANI composite solutions under humid conditions. The honeycomb‐patterned PANI–CTA composite films showed a high conductivity corresponding to about 1.5 S/cm, good mechanical stability, and high flexibility. The composites have a potential advantage comparing to pure PANI because of biodegradability and high solubility due to included CTA. These composite films can usefully be applied in the field of bio‐nanotechnology and medicine including micro‐structured electrode surfaces, filters for cell sorting, and bio‐interfaces and so on. POLYM. COMPOS., 37:2649–2656, 2016. © 2015 Society of Plastics Engineers