Preparation and characterization of polyaniline powder synthesized on microstructured aluminium

Aluminium surfaces were microstructured in 0.1 M HNO₃ by potentiodynamic anodic activation to potentials generating pitting. This surface was then used as an electrode to prepare polyaniline powder. The number of pits is responsible for the amount of powder produced. Emeraldine salt powder was successfully prepared from 0.4 M aniline in 0.5 M H₂SO₄ solution. Other acid solutions for deposition are not convenient because powders are electrochemically inactive (e.g., in 1 M HNO₃) or the electrode is covered by a film (e.g., in 0.5 M H₂C₂O₄).     

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

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

Monolayer and bilayer conducting polymer coatings for corrosion protection of steel in 1 M H2SO4 solution

In this study, monolayer polypyrrole (PPY), polyaniline (PANI), and bilayer PPY/PANI, PANI/PPY coatings were deposited onto steel electrodes by electropolymerization in 0.1 M monomer and 0.3 M oxalic acid solution. Such corrosion parameters of these electrodes, as corrosion potentials, anodic Tafel constants and corrosion current densities were determined by means of current–potential curves as a function of time in 1 M H₂SO₄ solution. These findings were compared to the corrosion parameters of a bare steel electrode in the same acid solution. The monolayer and bilayer polymer coatings were characterized by the Fourier transform infrared (FTIR) spectroscopy and SEM. Bilayer coatings displayed better corrosion inhibition efficiencies than monolayer coatings. Furthermore, the PPY/PANI coatings offered superior corrosion protection than the PANI/PPY coatings.     

Electrochemical synthesis of nanostructured polyaniline: Heat treatment and synergistic effect of simultaneous dual doping

Different nanostructured polyaniline (PAni) has been synthesized via facile template‐free electrochemical synthesis approach in aqueous medium. Instead of conventionally used aniline, aniline sulphate was used in electrochemical polymerization. The synthesis process involves simultaneous doping with combination of inorganic and organic acid, i.e., sulfuric acid (H₂SO₄) and p‐toluenesulfonic acid (PTSA) at different ratios keeping total dopant concentration constant. Synergistic increase in conductivity is observed and the best conductivity is achieved at 3:1 ratio of [H₂SO₄]:[PTSA]. Different nanostructures of PAni are revealed through morphological analysis consisting of nanosphere, nanorod, and clustered particles among which finer nanorods show the best electrical conductivity. Upon controlled heat treatment followed by further cooling, resistivity increases, but after one day it decreases again and in the optimized dual doped PAni, it approaches approximately the same value of initial resistance. Lattice strain and benzenoid to quinonoid ratio increases with heat treatment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of Dopant Ions on the Properties of Conducting Polyacrylamide/Polyaniline Hydrogels

Polyaniline-impregnated polyacrylamide conducting hydrogels have been synthesized chemically via interfacial polymerization route using different acidic doping agents like sulfuric acid (H₂SO₄), hydrochloric acid (HCl), and perchloric acid (HClO₄). The best properties were found in case of H₂SO₄-doped polyacrylamide/polyaniline sample when compared with other doping agents. The resulting hydrogel exhibits superior properties including compact structure, high crystallinity, good mechanical strength, and electrical conductivity. The maximum electrical conductivity of the order of 9.4 × 10^?5 S/cm was found in case of H₂SO₄ doped polyacrylamide/polyaniline.     

SORPTION OF PLATINUM,PALLADIUM, IRIDIUM,AND GOLD COMPLEXES ON POLYANILINE

ABSTRACT

Sorption of Pt, Pd, Ir and Au on polyaniline, synthesised by chemical oxidation of aniline in HC1, from HC1, LiC1 and H₂SO₄ solutions in the concentration range 0.1 to 10 mol dm^-3 has been studied. The as-prepared polyaniline (acid-PANI) and the one treated with 1 mol dm^-3 NH₄OH (base-PANl) have been used. Analysis of the data indicate that the AuC1₄ ^? species and negatively charged chloro-complexes of Pt and Pd are involved in the sorption process from HC1 solutions. Sorption of metal species from H₂SO₄ solutions is higher than that from HC1 solutions and negatively charged sulphate complexes of Pt and Pd are involved in the sorption     

Electrochemical Behavior of Polyaniline,Poly(o-Anisidine) and Their Copolymer Thin Films in Inorganic and Organic Supporting Electrolytes

Abstract

The influence of inorganic and organic supporting electrolytes on electrochemical, optical, and conducting properties of polyaniline, poly(o-anisidine), and poly(aniline-co-o-anisidine) thin films were investigated. Homo- and copolymer thin films were synthesized electrochemically, under cyclic voltammetric conditions in aqueous solutions of inorganic acids, viz., H₂SO₄, HCl, HNO₃, H₃PO₄, and HClO₄ and organic acids, viz., benzoic acid, cinnamic acid, oxalic acid, malonic acid, succinic acid, and adipic acid, at room temperature. The films were characterized by cyclic voltammetry, ultraviolet (UV)–Visible spectroscopy, and conductivity measurements using four probe technique. The optical absorption spectra indicated that the formation of the conducting emeraldine salt (ES) phase took place in all the inorganic supporting electrolytes used whereas, inorganic supporting electrolytes ES phase formed only with oxalic acid. It was also observed that the current density and conductivity of thin films are greatly affected by the nature and size of the anion present in the electrolyte. The formation of copolymer has also been confirmed by differential scanning calorimetry.     

Leaching kinetics of neodymium in sulfuric acid from E-scrap of NdFeB permanent magnet

The leaching kinetics of neodymium in NdFeB permanent magnet powder was analyzed for the purpose of recovery of neodymium in sulfuric acid (H₂SO₄) from E-scrap (electric scrap) of NdFeB permanent magnet powder treated by oxidation roasting to form a reactant. The reaction was conducted with H₂SO₄ concentrations ranging from 2.5 to 3.5M, a pulp density of 110.8 g/L, an agitation speed of 750 rpm, and a temperature range of 30 to 70 °C. After 4 h of leaching, the neodymium content in the E-scrap powders was completely converted into a neodymium sulfate (Nd₂(SO₄)₃) solution phase in H₂SO₄ in the condition of 70 °C and 3.0M H₂SO₄. Based on a shrinking core model with sphere shape, the leaching mechanism of neodymium was determined by the rate-determining step of the ash layer diffusion. Generally, the solubility of pure rare earth elements in H₂SO₄ is decreased with an increase in leaching temperatures. However, the leaching rate of the neodymium in E-scrap powders increased with the leaching temperatures in this study because the ash layer included in the E-scrap powder provided resistance against the leaching. Using the Arrhenius expression, the apparent activation energy values were determined to be 2.26 kJmol^?1 in 2.5M H₂SO₄ and 2.77 kJmol^?1 in 3.0 M H₂SO₄.     

The role of polyaniline salts in the removal of direct blue 78 from aqueous solution: A kinetic study

Three polyaniline salts (PANI–H₂SO₄, PANI–H₃PO₄, and PANI–HNO₃) have been synthesized by chemical oxidative polymerization of aniline. They have been tested as adsorbents for the removal of the textile dye direct blue 78 (DB78) from aqueous solution. The interaction followed pseudo-second-order kinetics whether the rate of interaction was measured from the depletion of dye concentration in solution or the increase in the amount of dye adsorbed on the PANI surface. The removal rate was a function of the activity of the polymer as well as the reaction parameters of the polymer/dye system. The activity of the PANI depended on the polymerization conditions. These conditions involve the concentration of aniline, ammonium peroxydisulfate as oxidant, and sodium dodecylsulfate (SDS), the type of dopant acid (H₂SO₄, H₃PO₄, HNO₃), and the polymerization time. Higher removal rate was observed at oxidant/aniline mole ratio equals 1. The rate of removal was in the order PANI–H₃PO₄ > PANI–H₂SO₄ > PANI–HNO₃. The rate decreased with increasing the concentration of DB78 and pH. It increased with increasing the load of PANI. Pseudo-second-order kinetics, external surface adsorption, and intraparticle diffusion models were concurrently operating in the removal of DB78 with PANI.     

High‐temperature oxidation of aniline to highly ordered polyaniline–sulfate salt with a nanofiber morphology and its use as electrode materials in symmetric supercapacitors

In this study, for the first time, aniline was oxidized by ammonium persulfate (APS) at higher temperatures without any protic acid, and APS acted as an oxidizing agent and a protonating agent. During the oxidation of aniline by APS, sulfuric acid formation occurred, and the sulfuric acid was incorporated into polyaniline (PANI) as a dopant. PANI–sulfate samples were characterized by IR spectroscopy, X‐ray diffraction, and scanning electron microscopy techniques. In this methodology, a highly ordered PANI–sulfate salt (H₂SO₄) with a nanofiber morphology was synthesized. Interestingly, a PANI base was also obtained with a highly ordered structure with an agglomerated netlike nanofiber morphology. PANI–H₂SO₄ was used as an electrode material in a symmetric supercapacitor cell. Electrochemical characterization, including cyclic voltammetry (CV), charge–discharge (CD), and impedance analysis, was carried out on the supercapacitor cells. In this study, the maximum specific capacitance obtained was found to be 273 F/g at 1 mV/s. Scan rate from cyclic voltammetry and 103 F/g at 1 mA discharge current from CD measurement. Impedance measurement was carried out at 0.6 V, and it showed a specific capacitance of 73.2 F/g. The value of the specific capacitance and energy and power densities for the PANI–H₂SO₄ system were calculated from CD studies at a 5‐mA discharge rate and were found to be 43 F/g, 9.3 W h/kg, and 500 W/kg, respectively, with 98–100% coulombic efficiency. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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

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

Polyaniline as corrosion inhibitor for iron in acid solutions

In recent years, polymer amines have been studied as an efficient corrosion inhibitor for iron in acid media. In this article, the performance of water soluble polyaniline as corrosion inhibitor for iron in 0.5M H₂SO₄ has been evaluated by potentiodynamic polarization, linear polarization, and electrochemical impedance spectroscopy and compared with the performance of the aniline monomer. It has been found that polyaniline is an efficient inhibitor, since the maximum efficiency of 84% has been observed at a concentration of 100 ppm, whereas the monomer has accelerated the corrosion. FTIR studies have shown that the polyaniline is strongly adsorbed on the iron surface and inhibits the corrosion effectively. However, aniline has been found to improve the passivation tendency of iron at higher concentrations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2144–2153, 2006     

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     

Study of Pb(II) in various H2O-H2SO4 mixtures by differential pulse polarography: solubility of lead sulphate,diffusion coefficient of Pb(II) and half-wave potential of Pb(Hg)/Pb(II)

A study of some properties of Pb(II) in solutions of sulphuric acid was carried out by means of differential pulse polarography. The range of concentrations of acid extended from 0.6 to 70 weight % of H₂SO₄ (0.06-11.5 M). Determination of the solubility of lead sulphate was found to be in good agreement with NBS's results in the range of H₂SO₄ concentrations they studied. With increasing concentration in H₂SO₄, the diffusion coefficient was found to decrease more than expected from the Stokes-Einstein equation, while the standard potential of Pb/Pb(II) related to she was found to increase. This led to a more important self-discharge of the negative electrode of the lead-acid battery.     

Preparation of Polyaniline/Mesoporous Silica Hybrid and Its Electrochemical Properties

Polyaniline/mesoporous silica hybrids were prepared by chemical modification with aniline and their capacitances were examined for application to electrode of electrochemical capacitor. The chemical modification was performed by two kinds of processes, polymer insertion into pores and in-situ polymerization within pores. In the case of the polymer insertion process, since the mean pore sizes of the hybrid did not change, polyaniline molecules were not inserted. On the other hand, in the case of the in-situ polymerization process, the mean pore sizes decreased from that of mesoporous silica, while the XRD patterns became broad. Therefore, aniline molecules polymerized in the inside of pores, however, the mesoporous silica collapsed in part. Maximum capacitance measured in 1 mol/l H₂SO₄ aqueous solution was around 226 F per unit mass of polyaniline.     

Synthesis and characterization of PANI nanostructures for supercapacitors and photoluminescence

Polyaniline structures were synthesized through a chemical method using citric acid and oxalic acid as carriers and 5???m size ??-alumina particles as a template. The obtained nano-size pristine products were characterized using X-ray diffraction, infrared spectroscopy, scanning electron microscopy, optical absorption spectroscopy, photoluminescence spectroscopy and cyclic voltammetry (CV). Nanofibrous PANI was obtained with oxalic acid, nanoparticles with oxalic acid and ??-alumina, net-like nanostructures with citric acid and spherical nanoparticles with citric acid and ??-alumina. The high intensity photoluminescence of PANI prepared with oxalic acid as a carrier is possibly due to greater chances of exciton formation resulting from increased ??-electron mobility. Electrochemical studies of PANI electrodes in 2.0?M H₂SO₄ were carried out at various scan rates. The CVs showed rectangular shape with added pronounced oxidation and reduction peaks.     

Electrosynthesis of poly(aniline-co-p-aminophenol) having electrochemical properties in a wide pH range

Copolymerization of aniline and p-aminophenol in aqueous sulfuric acid solutions was electrochemically performed using cyclic voltammetry on platinum electrodes. The monomer concentration ratio can strongly affect the copolymerization rate and electrochemical property of the copolymer. The optimum conditions for the copolymerization are that the potential sweep covers the −0.20 to 0.95 V (vs. SCE) potential range, and that a solution contains 0.18 M aniline, 0.02 M p-aminophenol and 0.50 M H₂SO₄. A resulting copolymer synthesized under the optimum conditions has a good electrochemical activity in 0.50 M solutions of Na₂SO₄ with pH ≤ 10.0. IR and XPS spectra indicate that -OH groups and SO₄²⁻ ions are contained in the resulting copolymer. The SEM images reveal that the microstructure of the copolymer depends on the monomer concentration ratio during the electrolysis.     

Corrosion inhibition by poly(N-ethylaniline) coatings of mild steel in aqueous acidic solutions

Poly(N-ethylaniline) (PNEA) coatings on mild steel have been electrodeposited from 0.1 to 0.5 M aqueous oxalic acid solutions containing 0.1 M N-ethylaniline (NEA) using potentiodynamic synthesis technique. The effect of oxalic acid concentration on the corrosion behavior of PNEA coated mild steel surfaces were investigated by DC polarization and electrochemical impedance spectroscopy (EIS) techniques in 0.1 M HCl and 0.05 M H₂SO₄ solutions. Corrosion test results showed that corrosion resistance of PNEA coatings decreases with increasing concentrations of oxalic acid in polymerization solution. Decreasing acidity of the polymerization solution causes more effective protection against corrosion in aqueous acidic corrosive medium.     

Electrochemical behaviors of polyaniline–poly(styrene‐sulfonic acid) complexes and related films

This research focuses on the syntheses of polyaniline with poly(styrenesulfonic acid) and their electrochemical behavior, including absorbance behavior and electrochemical response time of polyaniline‐poly(styrenesulfonic acid) [PANI–PSSA]. The complexes PANI–PSSA were prepared by electrochemical polymerization of monomer (aniline) with PSSA, using indium‐tin oxide (ITO) as working electrode in 1M HCl solution. Polyaniline (PANI), poly(o‐phenetidine)–poly(styrenesulfonic acid) [POP–PSSA], and poly(2‐ethylaniline)–poly(styrenesulfonic acid) [P2E‐PSSA] also were prepared by electrochemical polymerization and to be the reference samples. The products were characterized by IR, VIS, EPR, water solubility, elemental analysis, conductivity, SEM, and TEM. IR spectral studies shows that the structure of PANI–PSSA complexes is similar to that of polyaniline. EPR and visible spectra indicate the formation of polarons. The morphology of the blend were investigated by SEM and TEM, which indicate the conducting component and electrically conductive property of the polymer complexes. Elemental analysis results show that PANI–PSSA has a nitrogen to sulfur ratio (N/S) of 38%, lower than that for POP–PSSA (52%) and P2E–PSSA (41%). Conductivity of the complexes are around 10^?2 S/cm, solubility of PANI–PSSA in water is 3.1 g/L. The UV‐Vis. absorbance spectra of the hybrid organic/inorganic complementary electro‐chromic device (ECD), comprising a polyaniline–poly(styrenesulfonic acid) [PANI–PSSA] complexes and tungsten oxide (WO₃) thin film coupled in combination with a polymer electrolyte poly(2‐acrylamido‐2‐methyl‐propane‐sulfonic acid) [PAMPSA]. PANI–PSSA microstructure surface images have been studied by AFM. By applying a potential of ～3.0 V across the two external ITO contacts, we are able to modulate the light absorption also in the UV‐Vis region (200–900 nm) wavelength region. For example, the absorption changes from 1.20 to 0.6 at 720 nm. The complexes PANI–PSSA, POP–PSSA, and P2E–PSSA were prepared by electrochemical polymerization of monomer (aniline, o‐phenetidine, or 2‐ethylaniline) with poly(styrenesulfonic acid), using ITO as working electrode in 1M HCl solution, respectively. UV‐Vis spectra measurements shows the evidences for the dopped polyaniline system to be a highly electrochemical response time, recorded at the temperature 298 K, and the results were further analyzed on the basis of the color‐ discolor model, which is a typical of protontation systems. Under the reaction time (3 s) and monomer (aniline, o‐phenetidine, 2‐ethylaniline) concentration (0.6M) with PSSA (0.15M), the best electrochemical color and discolor time of the PANI–PSSA is slower than POP–PSSA complexes (125/125 ms; thickness, 3.00 μm) and P2E–PSSA complexes. Under the same thickness (10 μm), the best electrochemical color and discolor time of the PANI–PSSA complexes is 1500/750 ms, that is much slower than P2E–PSSA complexes (750/500 ms) and POP–PSSA complexes (500/250 ms). In film growing rate, the PANI–PSSA complexes (0.54 μm/s) are slower than P2E–PSSA complexes (0.79 μm/s) and POP–PSSA complexes (1.00 μm/s), it can be attributed to the substituted polyaniline that presence of electro‐donating (? OC₂H₅ or ? C₂H₅₎ group present in aniline monomer. The EPR spectra of the samples were recorded both at 298 K and 77 K, and were further analyzed on the basis of the polaron–bipolaron model. The narrower line‐width of the substituted polyaniline complexes arises due to polarons; i.e., it is proposed that charge transport take place through both polarons and bipolarons, compared to their salts can be attributed to the lower degree of structural disorder, the oxygen absorption on the polymeric molecular complexes, and due to presence of electro‐donating (? OC₂H₅ or ? C₂H₅) group present in aniline monomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:4023–4044, 2006     

Enrichment of chromium-content in passive layers on stainless steel coated with polyaniline

Enrichment of chromium-content in passive layers on a 304 stainless steel (SS) by coating polyaniline (PANI) has been confirmed by means of electrochemical and X-ray photoelectron spectroscope (XPS) techniques and thus prepared oxide films demonstrated to be highly stable in aggressive environment. PANI films are deposited on SS from a sulfuric acid solution with aniline monomer. The PANI-coated SS is found to maintain the passive state in a deaerated 1 M H₂SO₄ at 45 °C for several weeks. The passive state of SS remains in the same solution for several days even after the PANI films were completely removed. The passive layers underlying the PANI are certified to have higher chromium-content compared with the air-formed and anodically-formed oxide films on SS. It is suggested that PANI films enhance the passivation of SS by increasing the Cr₂O₃ content in the passive layer and by preventing the chromic oxide from directly interacting with aggressive solution.