Carbon fiber-polyaniline composites: Kinetics of electrodeposition of polyaniline onto carbon fibers by cyclic voltammetry

Homogeneous and uniform coatings of polyaniline were successfully deposited on carbon fibers by an aqueous electrodeposition technique using p-toluene sulfonic acid as the electrolyte. Electrochemical deposition of aniline was carried out by cyclic voltammetry in the potential range of ?0.2 V to 1.0 V versus saturated calomel electrode (SCE). The electrochemical deposition parameters such as the number of cycles, scan rate (SR), initial monomer ([M]), and electrolyte concentration ([E]) were systematically varied. The amount of composite coatings on carbon fibers was dependent on the electrochemical deposition parameters. From a weight gain analysis, the rate of the reactions (R p ) was calculated. As the aniline concentration was increased up to 0.35 M and electrolyte concentration up to 0.5 M, the deposition rate also increased, whereas an increase in scan rate decreased the deposition rate. Kinetic analysis showed that the rate equation for the p-toluene sulfonic acid system is R p ∝SR ?1.25 [M] 0.73 [E] 0.95 . IR spectra also showed an increase in the deposition of polyaniline coatings on carbon fibers with a decrease in the scan rate and an increase in both monomer and electrolyte concentration. The ratio of two oxidation states of polyaniline obtained during electrodeposition, namely emeraldine and pernigraniline, can be varied by changing the electrochemical deposition parameters.     

CARBON FIBER-POLYANILINE COMPOSITES: KINETICS OF ELECTRODEPOSITION OF POLYANILINE ONTO CARBON FIBERS BY CYCLIC VOLTAMMETRY

Homogeneous and uniform coatings of polyaniline were successfully deposited on carbon fibers by an aqueous electrodeposition technique using p-toluene sulfonic acid as the electrolyte. Electrochemical deposition of aniline was carried out by cyclic voltammetry in the potential range of -0.2 V to 1.0 V versus saturated calomel electrode (SCE). The electrochemical deposition parameters such as the number of cycles, scan rate (SR), initial monomer ([M]), and electrolyte concentration ([E]) were systematically varied. The amount of composite coatings on carbon fibers was dependent on the electrochemical deposition parameters. From a weight gain analysis, the rate of the reactions (R p ) was calculated. As the aniline concentration was increased up to 0.35 M and electrolyte concentration up to 0.5 M, the deposition rate also increased, whereas an increase in scan rate decreased the deposition rate. Kinetic analysis showed that the rate equation for the p-toluene sulfonic acid system is R p ∝SR -1.25 [M] 0.73 [E] 0.95 . IR spectra also showed an increase in the deposition of polyaniline coatings on carbon fibers with a decrease in the scan rate and an increase in both monomer and electrolyte concentration. The ratio of two oxidation states of polyaniline obtained during electrodeposition, namely emeraldine and pernigraniline, can be varied by changing the electrochemical deposition parameters.     

Electrosynthesis and capacitive performance of polyaniline–polypyrrole composite

The composite of polyaniline and polypyrrole (PPY‐PANI) was prepared by two‐step electrochemical polymerization method. Techniques of scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), and thermal gravity analysis (TG/DTG) measurements were used to characterize the morphology and structure of the composite. The electrochemical properties of the composite were investigated by cyclic voltammetry (CV), galvanostatic charge‐discharge, and electrochemical impedance spectroscopy (EIS). The results indicated that the polyaniline–polypyrrole composite showed better electrochemical capacitive performance than polypyrrole (PPY) and polyaniline (PANI). The specific capacitance of the composite electrode was 523 F/g at a current of 6 mA/cm² in 0.5 M H₂SO₄ electrolyte. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Electrocatalytic oxidation of cyclohexanol on a nickel oxyhydroxide modified nickel electrode in alkaline solutions

Electrocatalytic oxidation of cyclohexanol was investigated with cyclic voltammograms, linear galvanic voltammograms and chronoamperometric responses on a nickel oxyhydroxide modified nickel (NOMN) electrode prepared by cycling the potential of a nickel electrode in the potential range of 0.1 V to 0.6 V (vs SCE) in alkaline solutions. It was found that cyclohexanol was oxidized by NiOOH generated with further electrochemical oxidation of nickel hydroxide during the anodic potential sweep. One of the products of the reaction between cyclohexanol and NiOOH was Ni(OH)₂ which was subsequently oxidized to NiOOH on the anode. This resulted in the appearance of a new anodic peak in cyclic voltammograms compared with the absence of cyclohexanol and this anodic peak strongly depends upon potential scan rates and cyclohexanol concentrations. In addition, the presence of cyclohexanol in NaOH solutions also lead to the decrease of anodic potentials in linear galvanic voltammetric responses and the increase of current densities in chronoamperometric curves. Results showed that the oxidation of cyclohexanol on the NOMN electrode follows the catalytic reaction mechanism.     

Cyclic voltammetry and conductivity investigations of polyaniline

The cyclic voltammograms of polyaniline prepared electrochemically were examined in the range ?0.2 to 1.0 V vs. SCE in the presence and absence of aniline in the acqueous solution of HBF₄. Cyclic voltammetry studies show that the polymeric film suffers degradation when the potential exceeds +0.85 V, and below this potential, it is quite stable. The redox reaction of the film is reversible. The polymeric film synthesized at low temperature and high acid concentration exhibits higher electronic conductivities. © 1993 John Wiley & Sons, Inc.     

Electropolymerized polyaniline coatings on aluminum alloy 3004 and their corrosion protection performance

Homogeneous and adherent polyaniline coatings were electrosynthesized on aluminum (Al) alloy 3004 (AA 3004) from an aqueous solution containing aniline and oxalic acid by using the galvanostatic polarization method. A higher applied current density in the polymerization stage proved to be the best condition to adopt for the synthesis of more compact and strongly adherent polyaniline coatings on Al. The corrosion performances of polyaniline coatings were investigated in 3.5% NaCl solution by the potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS).Potentiodynamic polarization and electrochemical impedance spectroscopy studies reveal that the polyaniline acts as a protective layer on Al against corrosion in 3.5% NaCl solution. The current corrosion decreases significantly from 6.55 μA cm⁻² for uncoated Al to 0.158 μA cm⁻² for polyaniline-coated Al. The corrosion rate of the polyaniline-coated Al is found to be 5.17 × 10⁻⁴ mm year⁻¹, which is ∼40 times lower than that observed for bare Al. The potential corrosion increases from −1.015 V versus SCE for uncoated Al to ∼−0.9 V versus SCE for polyaniline-coated Al electrodes. The positive shift of ∼0.11 V in potential corrosion indicates the protection of the Al surface by the polyaniline coatings.The synthesized coatings were characterized by UV-visible absorption spectrometry, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Optical absorption spectroscopy reveals the formation of the emeraldine form of polyaniline. The results of this study clearly ascertain that the polyaniline has outstanding potential to protect the AA 3004 alloy against corrosion in a chloride environment.     

Detection and determination of CrVI in solution using polyaniline modified quartz crystal electrode

Conducting polymers such as polyaniline and polypyrrole exhibit novel sensoric properties and are able to interact chemically or electrochemically with the species of interest for detection. In the current investigation, construction of a sensor based on an electrochemical reaction between Cr^VI and a thin layer of polyaniline, coated at the surface of quartz crystal electrode, is reported. Polyaniline was synthesized, electrochemically, at the surface of quartz crystal electrode. It was then reduced at ?0.1 V versus Ag/AgCl. The modified electrode was exposed to various concentrations of Cr^VI solutions ranging from 10^?7 to 10^?1M. Mass changes of the polymer‐modified electrode due to the reaction between Cr^VI and polyaniline was found to be linear, corresponding to the concentration of Cr^VI. The experiments in both acidic and nonacidic conditions were performed. In both conditions, linear double‐loga thmic calibration curves of mass change of the polymer film versus Cr^VI concentration were obtained. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2772–2780, 2002     

Effect of process parameters on the electropolymerization potential and rate of formation of polypyrrole on stainless steel

Polypyrrole coatings were formed on stainless steel working electrodes in aqueous oxalic acid solution. The rate of formation of polypyrrole coatings on stainless steel increased proportionately with the current density but increased slightly with increased pyrrole concentration. Increasing oxalic acid concentration also had no significant change in the polymerization rate. The electropolymerization potential of pyrrole decreased significantly from 1.5 to 0.8 V versus SCE when the working electrode was polished. The polymerization potential, E_p, of pyrrole, increased however, with increased current density and decreased exponentially with the initial monomer and electrolyte concentration, respectively. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2433–2440, 1997     

Overoxidized poly(3,4-ethylenedioxythiophene)-overoxidized polypyrrole composite films with enhanced electrocatalytic ability for rutin and luteolin determination

In this study, a simple and effective method was proposed to improve the electrocatalytic ability of overoxidized poly(3,4-ethylenedioxythiophene)-overoxidized polypyrrole composite films modified on glassy carbon electrode for rutin and luteolin determination. The composite electrode was prepared by cyclic voltammetry copolymerization with LiClO₄-water as the supporting electrolyte. The peak current of rutin and luteolin on the composite electrode gradually decreased or even disappeared with the increase in the positive potential limit. After incubation in NaOH–ethanol solution with a volume ratio of 1:1, the composite electrodes prepared at positive potential limit greater than 1.5 V exhibited enhanced differential pulse voltammetry peak currents, reduced charge transfer resistance, larger effective specific surface area and higher electron transfer rate constant. The composite electrode prepared in the potential range of 0–1.7 V showed optimal electrocatalytic performance. The X-ray photoelectron spectroscopy results indicated that the content of –SO₂/–SO and –C=N– groups in the composite film increased significantly after incubation. Further, the Raman spectra and Fourier transform infrared spectra revealed that the thiophene ring structure changed from benzene-type to quinone-type, and the quinone-type pyrrole ring was formed. The electrocatalytic mechanism of the composite film was proposed based on the experimental results and further verified by Density Functional Theory calculation.     

Conducting polyaniline-nano-TiO2 composites for smart corrosion resistant coatings

Coatings prepared from polyaniline-nano-TiO₂ particles synthesized by in situ polymerization were found to exhibit excellent corrosion resistance much superior to polyaniline (PANI) in aggressive environments. The corrosion studies were carried out on steel plates coated with these formulations containing 10 wt% polyaniline prepared with different concentrations of nano-TiO₂. The electrochemical impedance spectroscopy was studied at periodic intervals during exposure to hot saline (65 °C) conditions for prolonged durations over a period of 90 h. The open circuit potential (OCP) was found to shift with time from −0.38 V SCE to more anodic side (−0.2 V SCE) much above that of bare steel (−0.5 V SCE). The presence of nano-TiO₂ was found to be vital in the prevention of corrosion and the shift of OCP to anodic side. From these data, one could envisage more than 100 times improvement in the corrosion resistance especially for polyaniline prepared with 4.18 wt% nano-TiO₂. The exceptional improvement of performance of these coatings has been associated with the increase in barrier to diffusion, prevention of charge transport by the nano-size TiO₂, redox properties of polyaniline as well as very large surface area available for the liberation of dopant due to nano-size additive.     

纳米TiO_2膜电极上乙醛酸的电催化合成研究

运用电化学循环伏安法 (CV)对纳米TiO2 膜电极 (Ti/nano TiO2 )在硫酸和草酸溶液中的电化学行为进行了研究。在c(H2 SO4 ) =1mol/L溶液中的循环伏安图上Epac1=- 0 .5 6V(vs.SCE)和Epac2 =- 0 96V(vs.SCE)处 ,出现两对可逆氧化还原峰 ,而在相同扫描速度下草酸溶液中的循环伏安曲线上 ,这两对电极反应氧化峰基本消失 ,还原峰电流增大 ,表明Ti/nano TiO2 膜电极对电还原草酸成为乙醛酸的反应具有较高的电催化活性和选择性。常温常压下 ,控制电位Epc=- 1 0V左右电解合成乙醛酸 ,乙醛酸的产率和电流效率分别达到 96 5 %和 90 %。     

Corrosion protection of 1Cr18Ni9Ti stainless steel by polypyrrole coatings in HCl aqueous solution

Electrically conducting polypyrrole (Ppy) coatings doped with sodium dodecylsulfate (SDS) have been deposited on 1Cr18Ni9Ti stainless steel by anodic polymerization from aqueous solutions of pyrrole and sodium dodecylsulfate. The corrosion behavior of Ppy coated steel was investigated in 0.3 M HCl aqueous solution at room temperature by a combination of electrochemical measurement techniques and scanning electron microscopy. The steel is in active state at the open circuit potential and suffers from pitting corrosion when the polarization potential is higher than 210 mV versus SCE. The Ppy coating can increase the corrosion potential of the steel by more than 600 mV versus SCE, and the pitting corrosion potential by more than 500 mV versus SCE. Fifty-day exposure experiments indicated that the Ppy coating shows high stability, and can inhibit effectively the corrosion of the steel.     

Electrochemistry of polyaniline: Study of the pH effect and electrochromism

Polyaniline was electrochemically synthesized from an aqueous medium with various acid electrolytes via potentiodynamic and potentiostatic techniques. The electrochemical synthesis of polyaniline was studied over various substrates, including Pt, Ti, Ni, and SnO₂ coated glass, and in various acid electrolytes. Cyclic voltammograms of electrochemically synthesized polyaniline were studied in HCl in a pH range of 1–4. Probable electrochemistry and chemical changes were deduced that occurred when polyaniline film was electrochemically oxidized and reduced between ?0.2 and 1.0 V versus a Ag/AgCl reference electrode in an acidic electrolyte at pH 1, and three corresponding oxidation and reduction peaks were described instead of two redox peaks (as observed by W. S. Huang, B. D. Humphrey, and A. G. MacDiarmid, J Chem Soc Faraday Trans 1 1986, 82, 2385). The electrochromic property was studied with changes in the chemical states of polyaniline during electrochemical oxidation and reduction. A new viscous electrolyte, aqueous AlCl₃ (pH 2), saturated with AgCl was used for the construction of an electrochromic display device. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 378–385, 2002     

Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries

A functional composite as anode materials for lithium-ion batteries, which contains highly dispersed TiO₂ nanocrystals in polyaniline matrix and well-defined mesopores, is fabricated by employing a novel one-step approach. The as-prepared mesoporous polyaniline/anatase TiO₂ nanocomposite has a high specific surface area of 224 m² g⁻¹ and a predominant pore size of 3.6 nm. The electrochemical performance of the as-prepared composite as anode material is investigated by cyclic voltammograms and galvanostatic method. The results demonstrate that the polyaniline/anatase nanocomposite provides larger initial discharge capacity of 233 mAh g⁻¹ and good cycle stability at the high current density of 2000 mA g⁻¹. After 70th cycles, the discharge capacity is maintained at 140 mAh g⁻¹. The excellent electrochemical performance of the polyaniline/TiO₂ nanocomposite is mainly attributed to its special structure. Furthermore, it is accessible to extend the novel strategy to other polymer/TiO₂ composites, and the mesoporous polypyrrole/anatase TiO₂ is also successfully fabricated.     

Removal of phenols from the aqueous solutions based on their electrochemical polymerization on the polyaniline electrode

Phenol and 3-nitrophenol in a aqueous solution of NaCl with pH 4.0 can be polymerized on the polyaniline electrode to form polyaniline/polyphenol and polyaniline/poly(3-nitrophenol) composites, respectively, using potential cycling between −0.20 and 1.00 V (vs. SCE). Polyaniline played an important role in lowering passivation of the electrode, which made the consecutive electrochemical polymerization of phenol and 3-nitrophenol become possible. The growth of the polyaniline/polyphenol and polyaniline/poly(3-nitrophenol) films in the electrolytic process was proved by the increasing area of the cyclic voltammograms as the electrolysis proceeded. The SEM images and IR spectra of polyaniline and phenolic polymers demonstrated the formation of the phenolic polymers on the polyaniline electrode. Therefore, the removal of both phenolic compounds is based on the formation of their polymers on the polyaniline film.     

Effect of the polymer layers and bilayers on the corrosion behaviour of mild steel: Comparison with polymers containing Zn microparticles

Electrodeposition methods have been used to obtain polypyrrole and polyaniline polymer layers, bilayers and blends of these polymers on carbon steel by passivation of the steel surface in the electrodeposition solution (oxalic acid and monomer) between −0.5 and 0.3 V versus Ag/AgCl and subsequent electrodeposition using different techniques (potentiodynamic, galvanostatic and potentiostatic). The results obtained indicate that prepassivation gives rise to adherent polymer layers with excellent corrosion resistance. Of all the bilayers obtained, the best results are yielded with those in which polyaniline is deposited as the base for the deposition of polypyrrole.

The electrodeposition of Zn microparticles on the previously deposited polymer layers promotes a great improvement in the corrosion current in highly aggressive solutions such as NaCl due to the effect of Zn as an anodic corrosion inhibitor. The drop in the corrosion rate depends on the amount of Zn deposited on the polymer layer, up to a certain point after which the protective effect ceases to be observed.     

Reversed micelle Synthesis of Ag/polyaniline nanocomposites via an in situ ultraviolet photo‐redox mechanism

Silver/polyaniline nanocomposites were synthesized in reversed micellar solution, and the reaction was performed via in situ reduction of silver nitrate in aniline by photolysis. The nanocomposites were characterized by ultraviolet‐visible spectroscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, thermo‐gravimetric analysis, differential scanning calorimetric analysis, and electrochemical methods. The results showed that the Ag/polyaniline nanocomposites are composed of nano‐sized particles of 15–30 nm that contain Ag domains of 10–15 nm. The electrical conductivity of an Ag/polyaniline pellet is 95.89 S cm⁻¹, whereas a polyaniline pellet is found to be 3.1 × 10⁻² S cm⁻¹. Ag/polyaniline composites also have a higher degradation temperature and specific capacitance, when compared with pure polyaniline. Potentiodynamic polarization showed the anodic shifting of the zero current potential and a lower exchange current density for the Ag/polyaniline composite. Compared with polyaniline, the Ag/polyaniline nanocomposite is a promising candidate for coatings with improved anticorrosion performance. POLYM. COMPOS.,, 2012. © 2012 Society of Plastics Engineers     

Inhibition of corrosion of mild steel by homopolymer and bilayer coatings of polyaniline and polypyrrole

Homopolymers and bilayers of polyaniline (PAni) and polypyrrole (PPy) coatings have been electropolymerized on mild steel by potentiodynamic synthesis technique in aqueous oxalic acid solutions. Characterization of coatings was carried out by cyclic voltammetry. Corrosion behavior of the polymer coated mild steel electrodes was investigated using linear anodic potentiodynamic polarization, Tafel test and electrochemical impedance spectroscopy (EIS) techniques in various aqueous corrosive solutions. Corrosion test results clearly showed that PPy and PAni/PPy bilayer coatings served as a stable host matrix on mild steel against corrosion. However, bilayers of PAni and PPy did not exhibit good combined properties of each polymer, unlike expected. PPy exhibited the best corrosion resistance among all coatings.     

Pronounced effect of the ionic liquid on the electrochromic property of the polyaniline film: Color changes in the wide wavelength range

The electrochemical polymerization of aniline in a solution consisting of 0.2 M aniline, 2 M H₂SO₄ and 30% ionic liquid (v/v), 1-ethyl-3-methylimidazolium ethyl sulfate (EMIES), was performed at a constant potential of 0.70 V versus SCE. The spectra of IR and ¹H NMR of the resulting product, PAnIL, indicate that the ionic liquid (IL) was incorporated into polyaniline during the polymerization process. The cyclic voltammograms of the PAnIL demonstrate that the electrochemical behavior of the PAnIL in the solutions of pH ≤ 3 is the same as that of polyaniline synthesized in the same conditions, but in the absence of the IL; however, the PAnIL in a solution of 0.3 M Na₂SO₄ with pH 12.0 still holds the redox activity. A significant result from the in situ spectroelectrochemical study shows that the absorption peak of the PAnIL film in a solution consisting of 0.3 M Na₂SO₄ and 20% IL (v/v) with pH 5.0 shifts from 509 to 890 nm, accompanied with the changes of colors from red-purple to violet, blue, green, greenish yellow and pale yellow, as the applied potential decreases from 0.70 to −0.10 V versus Ag/AgCl with saturated KCl solution, and vice versa. The response time is within 2 s for the color change of the PAnIL film from red-purple to pale yellow.     

Anodic, cathodic and cyclic voltammetric deposition of ruthenium oxides from aqueous RuCl3 solutions

Anodic, cathodic and cyclic voltammetric (CV) deposition of ruthenium oxides from aqueous RuCl₃ solutions have been investigated using stationary and rotating disk electrodes (RDE) in this work. The CV deposition behavior was examined using a RDE to differentiate the contribution of current from the reactions of ruthenium ions in the electrolyte and ruthenium oxides already adsorbed on the electrode. The results indicate that the CV growth of ruthenium oxides within the potential range of aqueous electrolyte decomposition is attributed to the anodic oxidation of ruthenium ions in the electrolyte. Cathodic deposition occurs only at potential negative than −0.30 V versus saturated calomel electrode (SCE) when H₂ evolves on the electrodes. Anodic deposition of ruthenium oxides can be obtained effectively in the potential range of ca. 0.9-1.1 V versus SCE, depending on the pH value of the electrolyte. The optimum anodic and cathodic deposition potential for maximum deposition efficiency is 1.0 and −0.9 V versus SCE, respectively, in the electrolyte solution of pH 2.