Electrical and humidity sensing properties of synthesized hydrophosphoric acid doped polyaniline

H₃PO₄ doped polyaniline was synthesized by a single‐step chemical polymerization method using ammonium persulfate as an oxidizing agent. The material characterization was done by SEM, UV–vis spectroscopy and thermogravimetric analysis (TGA). The pellets of the synthesized material were used to study the electrical properties, using a four‐probe method. The room temperature electrical conductivity is found to be 0.2201 S/cm. The electrical resistance in response to the varying humid environment (ranging between 20 and 100% RH) is recorded to evaluate the sensitivity of the H₃PO₄ polyaniline samples toward humidity. The resistance of the samples is found to vary by three orders of magnitude for 20–100% RH and is found to decrease with increasing humidity. The response and recovery time are observed to be 12–14 and 26–30 sec, respectively. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and characterization of polyaniline doped with organic acids

Spectroscopic [UV–visible and Fourier transform IR (FTIR)] and thermal properties of chemically synthesized polyanilines are found to be affected by varying the protonation media (acetic, citric, oxalic, and tartaric acid). The optical spectra show the presence of a greater fraction of fully oxidized insulating pernigraniline phase in polyaniline doped with acetic acid. In contrast, the selectivity in the formation of the conducting phase is higher in oxalic acid as a protonic acid media. The FTIR spectra of these polymers reveal a higher ratio of the relative intensities of the quinoid to benzenoid ring modes in acetic acid doped polyaniline. Scanning electron micrographs revealed a sponge‐like structure derived from the aggregation of the small granules in acetic acid and oxalic acid doped polyaniline. A three‐step decomposition pattern is observed in all the polymers, regardless of the protonic acid used for the doping. The second step loss related to the loss of dopant is found to be higher in the oxalic acid doped polymer. In accordance with these results the conductivity is also found to be higher in oxalic acid doped material. The temperature dependent conductivity measurements show the thermal activated behavior in all the polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2043–2049, 2004     

Synthesis,characterization, and hoping transport properties of HCl doped conducting biopolymer‐co‐polyaniline zwitterion hybrids

A series of electrically conductive zwitterion hybrid materials were facilely synthesized with anionic acacia gum (AG) and cationic HCl doped polyaniline (PANI) through radical copolymerization method. A representative acacia gum‐polyaniline hybrid (AG‐PANI) was characterized using UV‐vis, FTIR, ¹H NMR, and SEM. HCl doped AG‐PANI possesses zwitterion character due to the presence of NH on PANI and ? COO^? of AG. The cyclic voltammogram of AG‐PANI showed three anodic peaks at 0.20 V, 0.58 V, and 0.64 V along with two cathodic peaks at 0.50 V and 0.40 V with large capacitive background currents. AG‐PANI exhibited electrical conductivity that was found dependent on the ratio of aniline to AG, temperature, and pH. Its electrical conductivity versus temperature plot indicated Mott's nearest‐neighbor hopping mechanism at the temperature range 83–323 K. The hybridization of AG and PANI yielded eco‐friendly advanced functional materials for technological applications. Copyright © 2008 John Wiley & Sons, Ltd.     

The effect of supporting electrolyte on the electrochemical synthesis,morphology, and conductivity of polyaniline

Electrochemical synthesis of polyaniline (PANI) was carried out under cyclovoltammetric conditions using H₂SO₄, HCl, HNO₃, and HClO₄ as supporting electrolytes. The observed different rate of PANI deposit growth depending on the acid in the solution has been explained on the grounds of a different degree of specific adsorption for particular anion. It has been found that morphology of the deposit depends greatly upon the anion present in the solution. Thus, PANI synthesized from the solution of oxyacids results in a dense sponge-like structure while PANI from the hydrochloric acid solution results in a spaghetti-like structure. The structure of the deposit influences the conductivity, being higher for a dense deposit from oxyacid solutions and three orders of magnitude lower in case of a deposit from hydrochloric acid solution. © 1994 John Wiley & Sons, Inc.     

Polyurethane/polyaniline and polyurethane‐poly(methyl methacrylate)/polyaniline conductive core‐shell particles: Preparation,morphology, and conductivity

Polyurethane/polyaniline (PU/PANI) and polyurethane‐poly(methyl methacrylate)/polyaniline (PU‐PMMA/PANI) conductive core‐shell particles were synthesized by a two‐stage polymerization process. The first stage was to produce a core of PU or PU‐PMMA via miniemulsion polymerization using sodium dodecyl sulfate (SDS) as the surfactant. The second stage was to synthesize the shell of polyaniline over the surface of core particles. Hydrogen chloride (HCl) and dodecyl benzenesulfonic acid (DBSA) were used as the dopant agents. Ammonium persulfate (APS) was used as the oxidant for the polymerization of ANI. Different concentrations of HCl, DBSA, and SDS would cause different conformations of PANI chains and thus different morphologies of PANI particles. UV–visible spectra revealed that the polaron band was blue‐shifted because of the more coiled conformation of PANI chains by increasing the concentration of DBSA. Besides, with a high concentration of DBSA, both spherical‐ and rod‐shape PANI particles were observed by transmission electron microscope, and the coverage of PANI particles onto the core surfaces was improved. The key point of formation of rod‐type PANI particles was that DBSA was served with a high concentration accompanied with the existence of HCl or SDS. The better coverage of PANI particles over the core surfaces by charging higher DBSA concentrations resulted in a higher conductivity of hybrid particles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3902–3911, 2007     

Synthesis and characterization of single‐wall‐carbon‐nanotube‐doped emeraldine salt and base polyaniline nanocomposites

Nanocomposites of polyaniline (PANI) and single‐wall carbon nanotubes (SWNTs) were prepared and characterized via resonance Raman and electronic absorption spectroscopy (ultraviolet–visible/near‐infrared). The chemical synthesis of PANI was performed in the presence of SWNTs in concentrations ranging from 10 to 50 wt % (SWNT/PANI). The obtained materials were hydrophilic, homogeneous composite compounds. The chemical interaction between PANI (in the conducting emeraldine salt form and in the insulating emeraldine base form) and metallic and semiconducting nanotubes was investigated. The emeraldine salt form of the polymer was significantly stabilized in the composite in comparison with plain PANI. A selective electronic interaction process between PANI and metallic SWNTs was found. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 815–822, 2005     

Thermomechanical behaviors and dielectric properties of polyaniline‐doped para‐toluene sulfonic acid/epoxy resin composites

Composites based on conductive organic/inorganic fillers dispersed in insulating matrix have been widely investigated because of their widespread applications such as electromagnetic shielding, electrostatic discharge, and sensors. In this context, novel composite materials based on epoxy resin matrix charged with polyaniline (PANI)‐doped para‐toluene sulfonic acid were elaborated. Fourier transform infrared spectroscopy, X‐ray diffraction and scanning electron microscopy were used to check the structure and the morphology of the samples. Viscoelastic behavior and thermal stability of the composites were explored by dynamic mechanical thermal analysis and thermogravimetric analysis. It was shown that the PANI particles exhibited a partial crystalline structure and were homogeneously dispersed in epoxy matrix. Consequently, this structure affected the thermal stability and viscoelastic properties of the composites. Furthermore, the dielectric and electrical properties were investigated up to 1 MHz. Measurements of dielectric properties revealed that with loading fillers in matrix, the dielectric parameters increased to high values at low frequency then decreased at values around 40 and 32 of real and imaginary parts, respectively, at 1 MHz with 15% of PANI content. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis,characterization and X‐ray shielding properties of polypyrrole/lead nanocomposites

Novel radiation shielding nanocomposites based on a conducting polymer were fabricated and investigated to determine their abilities in attenuation of X‐rays. Polypyrrole/Pb nanocomposites were prepared through chemical reduction of lead salt by a facile solution‐phase method using t‐BuOLi‐activated LiH and in situ chemical polymerization of pyrrole in the presence of dodecyl benzene sulfonic acid as dopant and surfactant and iron chloride as the oxidant. The morphology, composition, and electrical conductivity of resulting products were characterized by scanning electron microscopy, transmission electron microscopy, X‐ray diffraction analysis, energy‐dispersive X‐ray spectroscopy, fourier transform infrared spectroscopy, and standard four‐wire technique, respectively. In order to evaluate capability of nanocomposites in radiation shielding, X‐ray photon interaction parameters such as linear attenuation coefficient, attenuation percentage, and half‐value thickness were determined for the samples with different Pb loadings and thicknesses, at photon energies of 13.95, 17.74, 20.08, 26.34, and 59.50 keV. The investigation was carried out to explore the potential of polypyrrole/Pb nanocomposites as thin and light‐weight radiation shielding materials. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and characterization of polyaniline: nanospheres,nanorods, and nanotubes—catalytic application for sulfoxidation reactions

The synthesis of nanostructured polyaniline (PANI) with different morphologies by simple alkali‐guided template‐free method followed by doping them with vanadium has been described. The synthesized polyaniline nanoparticles have been well characterized by various techniques. Further, the catalytic activity of the undoped and doped PANI nanostructures for selective oxidation of sulfides to sulfoxides in water has been studied. It was observed that the special morphology of nanostructures plays an important role in enhancement of catalytic activity. Vanadium‐doped PANI nanotubes and nanorods showed higher activity and selectivity than nanospheres. The catalyst has been reused for five consecutive cycles with consistent activity. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and characterization of C60/polyaniline composites from interfacial polymerization

C₆₀/polyaniline (PANI) nanocomposites have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in the presence of C₆₀ by using an interfacial reaction. When compared with the pure PANI nanofibers from the similar process, the diameter of the obtained C₆₀/PANI nanofibers was increased because of the encapsulation of C₆₀ into PANI during aniline polymerization, which resulted from the charge‐transfer interactions between C₆₀ and aniline fragment in PANI. In addition, the resulting C₆₀/PANI nanocomposites synthesized from the low initial C₆₀/aniline molar ratio (less than 1:25) showed the homogenous morphology composed of fiber network structures, which has an electrical conductivity as high as 1.1 × 10^?4 S/cm. However, the C₆₀/PANI nanocomposites from the higher initial C₆₀/aniline molar ratio (more than 1:15) showed the nonuniformly distributed morphology, and the electrical conductivity was decreased to 3.5 × 10^?5 S/cm. Moreover, the C₆₀/PANI nanocomposites from the interfacial reaction showed a higher value of electrical conductivity than the mechanically mixed C₆₀/PANI blends with the same C₆₀ content, because of the more evenly distributed microstructures. FTIR, UV–vis, and CV data confirmed the presence of C₆₀ and the significant charge‐transfer interactions in the resultant nanocomposites, which was responsible for the morphology development of the C₆₀/PANI and the variation of the electrical conductivity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis,characterization, and electrical properties of nanostructural polyaniline doped with novel sulfonic acids (4‐{n‐[4‐(4‐nitrophenylazo)phenyloxy]alkyl}aminobenzene sulfonic acid)

4‐{n‐[4‐(4‐Nitrophenylazo)phenyloxy]alkyl}aminobenzene sulfonic acid (Cn‐ABSA, where n = 2, 4, 6, 8, or 10) as a novel dopant for conducting polymers of polyaniline (PANI) was designed and synthesized. The molecular structure of Cn‐ABSA was characterized with ¹H NMR, Fourier transform infrared, and secondary‐ion mass spectrometry. Nanostructures (nanotubes or nanorods) of PANI–(Cn‐ABSA) were successfully synthesized with a self‐assembly process in the presence of Cn‐ABSA as the dopant. The morphology (shape and size) and conductivity of the resulting nanostructures strongly depended on the number of alkyl groups (n) and, in particular, the addition of water before polymerization. The formed micelles of aniline/Cn‐ABSA/water were proposed to be templatelike in forming PANI–(Cn‐ABSA) nanostructures on the basis of the emulsion properties measured by dynamic light scattering. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3485–3497, 2001     

Influence of phenylenediamine additions on the morphology and on the catalytic effect of polyaniline

The influence of para‐, ortho‐, and meta‐phenylenediamine (p‐, o‐, and m‐PDA) additions on the electrochemical synthesis of polyaniline has been investigated by the use of cyclic voltametry. It has been found that small additions (1 and 5 mmol L^?1) of PDA monomers influence significantly the polymerization rate. Whereas p‐PDA increases the polymerization rate, the addition of o‐ or m‐PDA slows it down. Therefore, a different number of potential cycling is necessary to obtain similar thickness of layers. The layers exhibit very different morphology, which changes from “spaghetti‐like” for polyaniline to “sponge‐like” for p‐PDA, to “pebble‐like” for o‐PDA and to “cauliflower‐like” for m‐PDA additions, respectively. The catalytic effect of the synthesized polymer layers has been tested. It has been found that all the layers exhibit catalytic effect in lowering the redox potential of hydroquinone/quinone tested reaction, but the rate of the electrocatalytic reaction varies depending on the PDA monomer added. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1599–1608, 2004     

Template‐Assisted Synthesis of Self‐Doped Polyaniline: Morphological Effects of Templates on the Conductivity

Self‐doped sulfonated polyaniline (PSA) has been synthesized on the surface of micellar nanoparticles made from positively charged surfactants by biocatalysis. The conformation forced by the electrostatic charge interactions between the positively charged micelle and the negatively charged PSA increases the conductivity of the PSA by three orders of magnitude. The pure PSA recovered from ion exchange, however, shows quite similar electrical properties compared with sulfonated polyanilines reported earlier. The increased conductivity of PSA complexes is as a result of the increased charge carrier concentration caused by a certain conformational locking.

     

PANI Conductivity: A Dependence of the Chemical Synthesis Temperature

Summary: This work evaluated the influence of the synthesis temperature on the polyaniline (PANI) properties obtained by in-situ polymerization onto a poly (terephthalate) (PET) substrate. The residual mass of these syntheses was dried under vacuum, obtaining PANI powders for each temperature investigated. PANI/PET thin films and PANI powders were characterized by atomic force microscopy (AFM), field emission scanning electron microscopy (FEG-SEM), X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-Vis) and four-point probe techniques. The UV-Vis results showed that the synthesized PANI presents the emeraldine oxidation state. By means of XRD technique, it was possible to verify that the PANI powders present crystalline form. The AFM and FEG-SEM techniques showed that the decrease in PANI/PET and PANI powders electrical conductivity with increasing of the synthesis temperature is related to the polymeric aggregates morphology.     

Electrically conductive,melt‐processed ternary blends of polyaniline/dodecylbenzene sulfonic acid,ethylene/vinyl acetate,and low‐density polyethylene

Although polyaniline (PANI) has high conductivity and relatively good environmental and thermal stability and is easily synthesized, the intractability of this intrinsically conducting polymer with a melting procedure prevents extensive applications. This work was designed to process PANI with a melting blend method with current thermoplastic polymers. PANI in an emeraldine base form was plasticized and doped with dodecylbenzene sulfonic acid (DBSA) to prepare a conductive complex (PANI–DBSA). PANI–DBSA, low‐density polyethylene (LDPE), and an ethylene/vinyl acetate copolymer (EVA) were blended in a twin‐rotor mixer. The blending procedure was monitored, including the changes in the temperature, torque moment, and work. As expected, the conductivity of ternary PANI–DBSA/LDPE/EVA was higher by one order of magnitude than that of binary PANI–DBSA/LDPE, and this was attributed to the PANI–DBSA phase being preferentially located in the EVA phase. An investigation of the morphology of the polymer blends with high‐resolution optical microscopy indicated that PANI–DBSA formed a conducting network at a high concentration of PANI–DBSA. The thermal and crystalline properties of the polymer blends were measured with differential scanning calorimetry. The mechanical properties were also measured. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3750–3758, 2004     

Synthesis and characterization of N‐substituted polyaniline with mesogen molecules

The N‐substituted polyaniline (PANi) was synthesized by incorporation of bromine‐terminated mesogens onto the emeraldine form of polyaniline. Firsty three liquid crystalline molecules containing biphenyl units were synthesized. These mesogenic molecules are named as: 6‐bromo‐ (4‐hexyloxy‐biphenyl‐4′‐oxy) hexane (C₆? C₆Br), 5‐bromo‐(4‐hexyloxy‐biphenyl‐4′‐oxy) pentane (C₆? C₅Br), 6‐bromo‐(4‐octyloxy‐biphenyl‐4′‐oxy) hexane (C₈? C₆Br). Differential scanning calorimetry (DSC) in combination with polarizing optical microscopy (POM) were used to investigate the thermal properties of them. Optical microscopy showed focal conic texture characteristic of the Smectic A phase for (C₆? C₅Br) and (C₈? C₆Br). For (C₆? C₆? Br) smectic phase was determined. DSC experiments were also found in accord with mesophase formation. For the synthesis of N‐substituted polyaniline with these mesogen molecules, the emeraldine base polyaniline was reacted with BuLi to produce the N‐anionic polyaniline and then deprotonated polyaniline was reacted with bromine‐end mesogen to prepare mesogen‐substituted polyaniline through N‐substitution reaction. The degree of N‐substitution can be controlled by adjusting the molar feed ratio of mesogen to the number of repeat units of PANi. The microstructure and compositions of obtained polymers were characterized by FT‐IR, elemental analysis, DSC, and scanning electron microscopy (SEM). The cyclicvoltammetry show that the electroactivity of N‐substituted polyaniline is strongly dependent on the degree of N‐grafting. The solubility of mesogen‐substituted polyaniline in common organic solvents such as THF and chloroform was improved by increasing the degree of N‐substitution and also the samples are partially soluble in xylene. Liquid crystalline behavior of mesogen‐substituted polyanilines was investigated via POM, but no mesophase was observed. Copyright © 2008 John Wiley & Sons, Ltd.     

Structural effects of dopants and polymerization methodologies on the solid‐state ordering and morphology of polyaniline

The solid‐state three‐dimensional ordering of polyaniline–dopant complexes was investigated with four structurally different sulfonic acid dopants. The doped materials were produced in three different ways: polyaniline emeraldine base doped with sulfonic acid (aqueous route), in situ polymerization at the organic–water solvent interface (interfacial route), and in situ polymerization in organic and aqueous solvent mixtures (bilayer route). p‐Toluenesulfonic acid (PTSA), 5‐sulfosalicilic acid (SSA), camphorsulfonic acid (CSA), and dodecylbenzene sulfonic acid (DBSA) were employed as dopants. The conductivity of the aqueous‐route samples showed 10 and 100 times higher conductivity than the interfacial and bilayer routes, respectively. WXRD studies suggested that the crystallinity of the doped samples was dependent on both the structure of the dopants and the polymerization techniques. DBSA increases the polyaniline interplanar distance and produced highly crystalline materials via the aqueous and bilayer routes but failed with the interfacial route because of poor solubility in water. CSA, PTSA, and SSA produced highly crystalline samples by the interfacial route but failed with the aqueous (except for CSA) and bilayer routes. SEM analysis revealed that the doped materials of the interfacial route had excellent continuous morphology and uniform submicrometer‐size particle distributions in comparison with those of the aqueous and bilayer routes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1321–1331, 2005     

Synthesis and Characterization of Conducting Polyaniline Doped with Polymeric Acids

Conducting polyaniline doped with polymeric acids was synthesized by a in situ chemical polymerization method. The synthesized polymers were characterized by using UV‐Visible, FT‐IR spectroscopy and SEM analysis. Thermal stability of these polymers was evaluated by using TGA/DSC analysis. Among the three polymeric acids used for doping purpose, poly(vinyl sulphonic acid) doped polyaniline is found to be more conducting than those doped with other acids. From the temperature dependent conductivity measurements, an increase in conductivity with increase in temperature was observed.     

Hierarchically‐ordered electroactive silica‐polyaniline nanohybrid: A novel material with versatile properties

Poly(trimethoxy silylpropylaniline), a nanoporous (pore diameter of 2.4 nm), electroactive (stable reversible redox characteristics), electrochromic (yellow at ?0.10 V, blue green at +0.50 V, and dark green at +0.70 V), and pH‐sensitive, silica–polyaniline (PANI) hybrid material (designated as KGM‐1) has been synthesized in powder form by a simple one‐pot chemical synthesis as well as a “thin nanolayered film” by cyclic voltammetry. High‐resolution transmission image of KGM‐1 informs that the particles are spherical, with diameters in the range of 0.5–1.5 μm. X‐ray diffraction pattern of pristine KGM‐1 confirms the combined presence of ordered silica network and PANI chains. The surface area of calcined KGM‐1 is 40 m²/g (～15 times higher than KGM‐1), and the average pore size is 2.4 nm. The N₂ adsorption features also inform that PANI is present as a uniform layer within the pores of silica and because of that the silica pores are not completely blocked. The reversible redox transitions in PANI units and nanoporosity of KGM‐1 are effectively used for the electro‐driven loading/release of DNA or adenosine 5′‐triphosphate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of phosphorized polyaniline doped with phytic acid and its anticorrosion properties for Mg-Li alloy

A phosphorized polyaniline (PANI) doped with phytic acid (PhA) was synthesized by the chemical oxide method with PhA as a dopant and applied to improve the anticorrosion properties of magnesium-lithium (Mg-Li) alloys after blending with eco-friendly silane sol. The chemical structures and morphologies of PANI samples were evaluated by FTIR spectroscopy, UV-Vis-NIR spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). All characterizations indicate that the as-synthesized phosphorized PANI (PANI-PhA) exists in doped emeraldine salt state with net-like structures crosslinked by phosphate carboxyl groups. The conductivity and thermostability of PANI-PhA were better than those of PANI doped with phosphoric acid (PANI-H₃PO₄) and undoped PANI. The anticorrosion properties of PANI/silane sol composite coatings for Mg-Li alloy were tested by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The results prove that the anticorrosion ability of PANI-PhA is the best among the three PANI samples, as shown by a low corrosion current (1.28 × 10^?7 A·cm^?2) and high impedance (5.62 × 10⁶ Ω·cm²). The possible anticorrosion mechanism was proposed based on procedure analysis.