Synthesis and studies of exceptionally crystalline polyaniline thin films

Highly crystalline camphor sulfonic acid (CSA)‐doped polyaniline (PANI) thin films cast from m‐cresol and N‐methylpyrrolidone (NMP) were investigated. PANI powder prepared by chemical oxidative polymerization subjected to doping–de‐doping–re‐doping procedures was cast into thin films using NMP and m‐cresol as solvents. X‐ray diffraction (XRD) reveals the presence of exceptionally highly crystalline or rather ordered regions in the PANI film samples prepared from m‐cresol. Atomic force microscopy (AFM) images also support the presence of crystalline regions on the surface of these films. The DC electrical conductivity of m‐cresol‐cast PANI is found to be quite high, and much higher than that of NMP‐cast PANI. The free‐carrier absorption tail extending to the near‐infrared region observed in the optical absorption spectrum of the m‐cresol‐cast PANI films suggests a metallic nature and regular structural arrangement in these films. Both inter‐chain and intra‐chain ordering brought about as a result of CSA doping, secondary doping effect of m‐cresol and ultrasonication are suggested to be the prime factors contributing towards the observed excellent crystallinity of these PANI films as evident from the XRD and AFM studies. The marked thermal stability of the m‐cresol‐cast PANI films is also established based on the variation of DC electrical conductivity with temperature and on thermogravimetric analysis. Copyright © 2012 Society of Chemical Industry     

Synthesis and characterization of tanninsulfonic acid doped polyaniline–metal oxide nanocomposites

Composites of conducting polymers and metal oxides have a potential role in electronic devices because of their enhanced physical and electronic properties. An in situ synthesis of metal oxide nanocomposites of polyaniline (PANI) and tanninsulfonic acid doped PANI was carried out at ?10°C with two different ratios of aniline to sodium persulfate (oxidant) and the simultaneous incorporation of TiO₂, Al₂O₃, and ZnO nanopowders. The products were characterized by X‐ray diffraction (XRD), thermal analysis, spectroscopy, and electrical conductivity measurements. XRD and thermogravimetric analysis confirmed the presence of the metal oxide in the final product, whereas the spectroscopic characterization revealed interactions among the tannin, metal oxides, and PANI. The electrical properties were determined by four‐point‐probe bulk conductivity measurements. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

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     

Polyaniline/polyimide blends as gas sensors and electrical conductivity response to CO–N2 mixtures

The effects of dopant type, doping level, polyimide (PI) content and temperature on electrical conductivity response of polyaniline (PANI) and polyaniline/polyimide (PANI/PI) blends to CO–N₂ gas mixtures were systematically investigated. At the same doping level, HNO₃‐doped PANI has a greater electrical conductivity response and sensitivity towards CO than that of camphor sulfonic acid (CSA)‐doped PANI because the former has a more ordered structure. The interaction mechanism between CO and PANI is proposed to occur at the attack site, ? N?H? or the amine nitrogen where CO withdraws an electron. Addition of PI causes a small change in electrical conductivity under atmospheric conditions when PI content is below the percolation threshold value of 55 wt%. Addition of PI reduces brittleness and improves electrical conductivity sensitivity towards CO; the effect is more pronounced at higher temperatures. Copyright © 2005 Society of Chemical Industry     

Preparation and properties of 8‐hydroxyquinoline aluminum quinoline/polyaniline core–shell composite

Polyaniline (PANI) as an excellent conducting polymer material has been used to synthesize 8‐hydroxyquinoline aluminum quinoline/polyaniline (Alq₃/PANI) composites with core‐shell structure which is expected to form ultra‐conjugated system between core/shell and be used as organic electronic material. Alq₃ was coated by sodium dodecyl benzene sulfonate doped PANI via in situ polymerization of aniline on the surface of Alq₃. The morphology, structure crystallinity, and thermal stability of synthesized composite were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and thermal gravimetric analysis. Results indicated that the composite is core‐shell structure and exhibits good thermal stability. Conductivity of composite was investigated and showed that Alq₃ as core in composite which improved the conductivity of pristine PANI, indicating that electronic interactive effect was formed between core and shell. POLYM. COMPOS., 36:272–277, 2015. © 2014 Society of Plastics Engineers     

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     

Synthesis and characterization of self‐doped poly(aniline‐co‐aminonaphthalene sulfonic acid) nanotubes

Self‐doped poly(aniline‐co‐aminonaphthalene sulfonic acid) (PANI‐ANSA) was synthesized by the copolymerization of 5‐aminonaphthalene‐2‐sulfonic acid (ANSA) and aniline. Scanning electron microscopy and transmission electron microscopy showed that the morphology of PANI‐ANSA synthesized at a high molar ratio of aniline to ANSA was nanotubular, but at a low molar ratio, only a granular morphology formed. A possible formation mechanism for nanotubes was proposed. PANI‐ANSA had better thermal stability than HCl‐doped polyaniline; the highest onset decomposition temperature was as high as 340°C because of ? SO₃H linked with the polymer backbone by a covalent bond. PANI‐ANSA was partially soluble in basic solutions, and its conductivity was between 10^?2 and 10^?4 S/cm, depending on the sulfonation degree. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1297–1301, 2003     

Solid polymer electrolytes. XI. Preparation,characterization and ionic conductivity of new plasticized polymer electrolytes based on chemical‐covalent polyether–siloxane hybrids

A new hybrid polymer electrolyte system based on chemical‐covalent polyether and siloxane phases is designed and prepared via the sol–gel approach and epoxide crosslinking. FT‐IR, ¹³C solid‐state NMR, and thermal analysis (differential scanning calorimetry (DSC) and TGA) are used to characterize the structure of these hybrids. These hybrid films are immersed into the liquid electrolyte (1M LiClO₄/propylene carbonate) to form plasticized polymer electrolytes. The effects of hybrid composition, liquid electrolyte content, and temperature on the ionic conductivity of hybrid electrolytes are investigated and discussed. DSC traces demonstrate the presence of two second‐order transitions for all the samples and show a significant change in the thermal events with the amount of absorbed LiClO₄/PC content. TGA results indicate these hybrid networks with excellent thermal stability. The EDS‐0.5 sample with a 75 wt % liquid electrolyte exhibits the ionic conductivity of 5.3 × 10^?3 S cm^?1 at 95°C and 1.4 × 10^?3 S cm^?1 at 15°C, in which the film shows homogenous and good mechanical strength as well as good chemical stability. In the plot of ionic conductivity and composition for these hybrids containing 45 wt % liquid electrolyte, the conductivity shows a maximum value corresponding to the sample with the weight ratio of GPTMS/PEGDE of 0.1. These obtained results are correlated and used to interpret the ion conduction behavior within the hybrid networks. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1000–1007, 2006     

Novel chemically synthesized polyaniline electrodes containing a fluoroboric acid dopant for supercapacitors

The performance of chemically synthesized dual‐acid‐doped polyaniline (PANI) electrode material was investigated for supercapacitors for the first time. Three different grades of PANI‐containing fluoroboric acid (HBF₄) as one of the dopants were prepared by a chemical polymerization method. PANI–dodecylhydrogen sulfate–HBF₄ salt was synthesized by an emulsion polymerization pathway. A PANI–HBF₄–sodium tetrafluoroborate composite and PANI–HBF₄ salt were prepared from different modifications of dopants by a dedoping–redoping process. Capacitative behaviors of the three grades of PANI electrode materials were investigated. Among the three different grades of PANI, PANI–HBF₄ electrode showed the best performance in terms of conductivity (2.3 × 10^?1 S/cm), specific capacitance of the supercapacitor (140 F/g), specific energy (9.6 W h/kg), and specific power (58.8 W/kg). An increase in the capacitance of PANI–HBF₄ was achieved, which identified the significant contribution of the dedoping–redoping processes in the PANI system for supercapacitors. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal behavior of polyaniline films and polyaniline–polystyrene blends

In this article, a study of the thermal behavior of polyaniline films and polyaniline–polystyrene blends is presented. Transport measurements (electrical conductivity and thermoelectric power) at high temperature and thermogravimetric analysis show that an irreversible degradation is observed near 450 K for films doped with DiOHP and near 500 K for films doped with CSA. In both cases, the thermoelectric power is the most sensitive parameter to electrical degradation during the heating of conducting films. Electrical conductivity measurements during heating–cooling cycles show a diminution of the room temperature conductivity after evaporation of the solvent (water, m‐cresol). A model of cluster with a variable diameter allows interpreting this phenomenon by assuming the existence of a sensitive frontier to the solvent at the periphery of conducting clusters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1848–1855, 2002; DOI 10.1002/app.10468     

Effect of Ni2+ as a codopant on the structure,morphology, and conductivity of nanostructured polyaniline

One‐dimensional nanostructures of polyaniline (PANI) doped with (1S)‐(+)‐10‐camphorsulfonic acid (D‐CSA) alone and with NiCl₂ as a codopant were synthesized via in situ polymerization. PANI nanofibers with diameters of about 200 nm were formed when PANI was doped with D‐CSA only. When NiCl₂ was added as a codopant, the morphology of PANI obviously changed. The effects and related mechanisms were investigated by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, inductively coupled plasma–atomic emission spectroscopy, and X‐ray diffraction, and the results indicated that Ni²⁺ destroyed the micelles' structure by chemical conjunction with ? SO₃H groups in camphorsulfonic acid (CSA) molecules, which were the key component in forming the CSA–aniline micelles. The combination between Ni²⁺ and SO in CSA with a lower addition of Ni²⁺ led to a reduction of CSA doping to PANI, but a higher loading of Ni²⁺ brought about the direct doping of Ni²⁺ to PANI, which caused a higher degree of doping and oxidation. The conductivity of PANI increased almost linearly with increasing Ni²⁺. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Environmental stability of electrically conductive viologen–polyaniline systems

Viologen–polyaniline (PANI) systems were prepared by PANI being coated onto viologen‐grafted low‐density polyethylene films. PANI in this system could undergo photoinduced doping with ultraviolet irradiation. The electrical stability of the electrically conductive viologen–PANI systems was found to be stable in air, but the conductivity decreased rapidly when the sample was treated in aqueous media of pH > 5 because of the migration of the anions out of PANI into water. However, the conductivity increased by a factor of 2 after treatment in a 1M HCl solution because of the further protonation of PANI by acid. The structural changes of these systems were monitored with ultraviolet–visible absorption spectroscopy, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and resistance measurements. The electrical stability of the viologen–PANI system in water could be enhanced via spin coating with poly(methyl methacrylate) (PMMA) because this layer inhibited the migration of the anions out of the system. The photoinduced doping of PANI could be carried out either before or after the spin coating of PMMA. The advantages and limitations of each method were demonstrated. A PMMA coating with a thickness of approximately 10 μm allowed a significant doping level to be achieved within a short period of irradiation and, at the same time, effectively shielded the film from the effects of the aqueous medium. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2099–2107, 2002     

Dielectric properties of lithium‐perchlorate‐filled acrylonitrile–hexyl methacrylate copolymer films

A series of poly(acrylonitrile‐co‐hexyl methacrylate), PAN‐co‐PHMA, copolymers with various hexyl methacrylate (HMA) contents were synthesized by emulsion technique. The incorporation of HMA units into the copolymers was confirmed by Fourier transform infrared and proton nuclear magnetic resonance (¹H‐NMR) spectroscopy. Glass transition temperatures (T _g) and thermal decomposition temperatures of copolymers were determined by differential scanning calorimetry and thermogravimetric analysis. The T _g of copolymers were lowered monotonically by increasing HMA content, while thermal stabilities of copolymers were enhanced. The frequency dependence of dielectric properties of three different amounts of LiClO₄ salt doped copolymer films was investigated. The influence of molar fraction of HMA on dielectric constant and ac‐conductivity of copolymer films was examined. Samples with higher HMA contents showed better stability and conductivity, as a result of increase in free volume and the mobility of the dipoles. The ac conductivity of copolymers was also improved by increasing LiClO₄ salt which was due to the existence of more charge carriers. PAN(88)‐co‐PHMA(12) copolymer with 1.5 mol% of lithium salt exhibited ionic conductivity of the 7.8 × 10⁻⁴ S/cm at 298 K. POLYM. COMPOS., 38:1792–1799, 2017. © 2015 Society of Plastics Engineers     

Preparation and self‐assembly of polyaniline nanorods and their application as electroactive actuators

To improve the performance of ion‐exchange polymer–metal composite (IPMC) actuators, an electrical pathway material for enhancing the surface adhesion between the membrane and the metal electrodes of the IPMC was studied. As an efficient electrical pathway material, polyaniline nanorods (PANI‐NRs) doped with p‐toluene sulfonic acid (TSA) were synthesized with a template‐free method. The factors affecting polyaniline morphology were studied with various dopant concentrations and oxidant feeding rates. Highly conductive PANI‐NRs were formed when they were synthesized with ammonium persulfate at a 5.0 mL/min oxidant feeding rate and doped with 0.125M TSA. The conductivity of the PANI‐NRs was 1.15 × 10^?1 S/cm, and their diameters and lengths were 120–180 nm and 0.6–2 μm, respectively. To apply the membrane as an actuator, perfluorosulfonated ionomer (Nafion)/PANI‐NR blends were prepared by solution blending and casting. The actuating ability of the three‐layered membrane consisting of Nafion/PANI‐NR blends was then examined and compared with that of Nafion only. The actuating ability of the IPMC was improved when Nafion/PANI‐NRs were used as electrical pathways. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Correlating structure with ionic conductivity in bis(phosphonium)‐containing [NTf2] thiol–ene networks

Thiol–ene photopolymerization was employed in order to prepare a series of covalently crosslinked bis(phosphonium)‐containing poly(ionic liquid) (PIL) networks. While the counteranion was held constant (NTf₂), the structure of the bis(phosphonium)‐containing ‘ene’ monomer was varied in order to explore the breadth of thermal, mechanical and conductive properties available for this system. Towards this end, it was determined that more flexible spacers within the cationic monomer led to PIL networks with lower T_g values and higher conductivities. Most notable was a two‐ to three‐orders‐of‐magnitude increase in ionic conductivity (from 10^?9 to 10^?6 S cm^?1 at 30 °C, 30% relative humidity) when the R group on phosphonium was changed from phenyl to isopropyl. Changing the functional group ratio to off‐stoichiometry also led to a slight increase in conductivity. Although the thermal stability (T_d5%) of the phosphonium ionic liquid monomers was found to be significantly higher (>400 °C) than that of analogous imidazolium monomers, this improvement was not observed to directly transfer over to the polymer where a two‐step decomposition pathway was observed. The first step is attributed to the thiol monomer backbone while the second step correlates well with decomposition of the phosphonium portion of the PIL. © 2019 Society of Chemical Industry     

Synthesis of copper chloride and cobalt chloride doped polyanilines and their magnetic and alternating‐current transport properties

Polyaniline (PANI) was synthesized by the well‐known oxidative polymerization of aniline with ammonium peroxodisulfate as the oxidant. The morphological, structural, thermal, optical, magnetic, and electrical properties were characterized with scanning electron microscopy, X‐ray diffraction, Fourier transform infrared, thermogravimetric analysis, differential scanning calorimetry, ultraviolet–visible spectroscopy, room‐temperature magnetic measurements, and low‐temperature electrical transport measurements by the standard four‐probe method. Greater thermal stability and crystallinity were observed in doped PANI versus pure PANI. Magnetic measurements showed that the magnetic susceptibility was field‐dependent. Positive and negative susceptibility values were observed. This may have been due to the interactions of magnetic ions among interchains or intrachains of the polymer matrix. The alternating‐current (ac) conductivity was measured in the temperature range of 77–300 K in the frequency range of 20 Hz to 1 MHz. The frequency‐dependent real part of the complex ac conductivity was found to follow the universal dielectric response: σ′(f) ∝ f^s [where σ′(f) is the frequency‐dependent total conductivity, f is the frequency, and s is the frequency exponent] The trend in the variation of the frequency exponent with temperature corroborated the fact that correlated barrier hopping was the dominant charge‐transport mechanism for PANI–CoCl₂. An anomalous dependence on temperature of the frequency exponent was observed for PANI–CuCl₂. This anomalous behavior could not be explained in terms of existing theories. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication of core–shell nanocomposites with enhanced photocatalytic efficacy

The current study establishes the unprecedented involvement in the evolution and production of novel core–shell nanocomposites composed of nanosized titanium dioxide and aniline‐o‐phenylenediamine copolymer. TiO₂@copoly(aniline and o‐phenylenediamine) (TiO₂@PANI‐o‐PDA) core–shell nanocomposites were chemically synthesized in a molar ratio of 5:1 of the particular monomers and several weights of nano‐TiO₂ via oxidative copolymerization. The construction of the TiO₂@PANI‐o‐PDA core–shell nanocomposites was ascertained from Fourier transform IR spectroscopy, UV–visible spectroscopy and XRD. A reasonable thermal behavior for the original copolymer and the TiO₂@PANI‐o‐PDA core–shell nanocomposites was investigated. The bare PANI‐o‐PDA copolymer was thermally less stable than the TiO₂@PANI‐o‐PDA nanocomposites. The core–shell feature of the nanocomposites was found to have core and shell sizes of 17 nm and 19–26 nm, respectively. In addition, it was found that the addition of a high ratio of TiO₂ nanoparticles increases the electrical conductivity and consequently lowers the electrical resistivity of the TiO₂@PANI‐o‐PDA core–shell nanocomposites. The hybrid photocatalysts exhibit a dramatic photocatalytic efficacy of methylene blue degradation under solar light irradiation. A plausible interpretation of the photocatalytic degradation results of methylene blue is also demonstrated. Our setup introduces a facile, inexpensive, unique and efficient technique for developing new core–shell nanomaterials with various required functionalities and colloidal stabilities. © 2018 Society of Chemical Industry     

Spectroscopic,electrical, and relaxor‐like properties of cellulose acetate–erbium (III) chloride composite films

Cellulose acetate thin films doped with erbium (III) chloride (ErCl₃) of different concentrations were prepared by the solution method. The prepared composite films were characterized using scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis. IR spectral analysis, UV–visible absorption, a.c. conductivity, and dielectric properties were investigated. The studied ErCl₃‐doped samples showed different properties from those of their pure components. SEM micrographs showed that for small dopant concentrations, samples tend to form conducting nanostructures with negligible particle agglomeration. DSC showed a monotonic development of the glass transition temperature by increasing the concentration of dopant material. Variation in the height, shape, and position of the bands in infrared transmission spectra, as well as the glass transition temperatures, indicated a complex interaction with the polymer molecular chains. Thermal stability and thermodynamic parameters were found to be concentration dependent. The electronic transitions’ band gabs and energy tails were calculated from the optical data. The dielectric studies showed that the correlated barrier hopping model was the dominant mechanism of a.c. conductivity. We found that samples with 10% and 20% ErCl₃ exhibited high dielectric constants and have pronounced electrostriction and relaxor‐like properties. Such samples can be used in many applications like electromechanical and thermomechanical transducers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45220.     

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