Electrochemical synthesis and corrosion protection properties of poly(o‐toluidine) coatings on low carbon steel

Uniform and strongly adherent poly(o‐toluidine) (POT) coatings have been synthesized on low carbon steel (LCS) substrates by electrochemical polymerization (ECP) of o‐toluidine under cyclic voltammetric conditions from an aqueous sodium tartrate solution. Cyclic voltammetry (CV), UV‐visible absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD) measurements, and scanning electron microscopy (SEM) were used to characterize these coatings, which indicates that the sodium tartrate is a suitable medium for the ECP of o‐toluidine and it occurs without noticeable dissolution of LCS. Corrosion protection properties of the POT coatings were evaluated in aqueous 3% NaCl by the potentiodynamic polarization measurements and CV. The result of the potentiodynamic polarization demonstrates that the POT coating has ability to protect the LCS against corrosion. The corrosion potential was about 334 mV more positive in aqueous 3% NaCl for the POT‐coated LCS than that of bare LCS and reduces the corrosion rate of LCS almost by a factor of 50. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 685–695, 2005     

Synthesis of poly(aniline‐co‐o‐toluidine) coatings and their corrosion‐protection performance on low‐carbon steel

Strongly adherent poly(aniline‐co‐o‐toluidine) coatings were synthesized on low‐carbon‐steel substrates by the electrochemical copolymerization of aniline with o‐toluidine with sodium tartrate as the supporting electrolyte. These coatings were characterized with cyclic voltammetry, ultraviolet–visible absorption spectroscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and scanning electron microscopy. The formation of the copolymer with the mixture of monomers in the aqueous sodium tartrate solution was ascertained by a critical comparison of the results obtained from the polymerizations of the individual monomers, aniline and o‐toluidine. The optical absorption spectrum of the copolymer was drastically different from the spectra of the respective homopolymers, polyaniline and poly(o‐toluidine). The extent of the corrosion protection offered by poly(aniline‐co‐o‐toluidine) coatings to low‐carbon steel was investigated in aqueous 3% NaCl solutions by open‐circuit‐potential measurements and a potentiodynamic polarization technique. The results of the potentiodynamic polarization measurements showed that the poly(aniline‐co‐o‐toluidine) coatings provided more effective corrosion protection to low‐carbon steel than the respective homopolymers. The corrosion rate depended on the feed ratio of o‐toluidine used for the synthesis of the copolymer coatings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:1868–1878, 2007     

Glucose oxidase electrodes of poly(o‐anisidine), poly(o‐toluidine), and their copolymer as biosensors: A comparative study

Thin films of poly(o‐anisidine) (POA), poly(o‐toluidine) (POT), and their copolymer poly(o‐anisidine‐co‐o‐toluidine) (POA‐co‐POT) were electropolymerized in solutions containing 0.1M monomer(s) and 1M H₂SO₄ as an electrolyte through the application of a sequential linear potential scanning rate of 50 mV/s between ?0.2 and 1.0 V versus an Ag/AgCl electrode on a platinum electrode. A simple technique was used to construct glucose sensors through the entrapment of glucose oxidase (GOD) in thin films of POA, POT, and their copolymer POA‐co‐POT, which were electrochemically deposited on a platinum plate in phosphate and acetate buffers. The maximum current response was observed for POA, POT, and POA‐co‐POT GOD electrodes at pH 5.5 and at a potential of 0.60 V (vs Ag/AgCl). The phosphate buffer yielded a fast response in comparison with the acetate buffer in amperometric measurements. The POT GOD electrode showed a fast response and was followed by POA‐co‐POT and POA GOD electrodes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1877–1884, 2004     

A simple one‐step chemical route to gold/polymer core/shell composites and polymer hollow spheres

Au/poly(o‐toluidine) (POT) core/shell composite spheres have been successfully fabricated by chemical polymerization route in aqueous solution without the aid of surfactant or functional acids using HAuCl₄ as the oxidant. By altering the concentration of oxidant, the amount of Au nanoparticles inside each POT sphere can be tuned from tens to one. Moreover, uniform POT hollow spheres with one opening in each polymer surface can be obtained under extremely low concentration of oxidant. The chemical structures of Au/POT composites were confirmed by Fourier transform infrared (FTIR), UV‐vis, and X‐ray diffraction (XRD) spectroscopies. Moreover, the formation mechanisms of Au/POT core/shell composites and POT hollow spheres were also discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Peroxomonosulphate initiated graft copolymerization of o‐toluidine onto nylon 6 and wool fibers—A kinetic approach

Chemical polymerization of o‐toluidine (OT) in the presence of nylon 6 and wool fibers initiated by peroxomonosulphate (PMS) in an aqueous acidic medium was carried out under nitrogen atmosphere. During the polymerization process, graft copolymers were formed along with homopolymers of OT. A procedure is given for the separation of poly(o‐toluidine) (POT) grafted fiber from the homopolymer. Rate of homopolymerization (R_h), rate of grafting (R_g), percentage grafting, and percentage grafting efficiency were determined. Rate constants were evaluated from the experimental results. The chemical grafting of POT onto nylon 6 and wool fibers was confirmed through Fourier transform infrared (FTIR) spectroscopy and electrical conductivity measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2317–2326, 2002     

Synthesis and characterization of phosphorus‐containing polystyrene

Poly(o‐toluidine) ( POT) has been electrodeposited on brass from an aqueous salicylate solution by using cyclic voltammetry, and its corrosion protection performance has been evaluated by potentiodynamic polarization technique and electrochemical impedance spectroscopy in aqueous 3% NaCl solution. The corrosion potential was about 0.115 V vs. SCE more positive for the POT‐coated brass than that of uncoated brass and reduces the corrosion rate of brass almost by a factor of 800. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrochemical synthesis of poly(indole‐co‐thiophene) on low‐nickel stainless steel and its anticorrosive performance in 0.5 mol L−1 H2SO4

The electrochemical synthesis of poly(indole‐co‐thiophene) copolymer coatings was achieved on low‐nickel stainless steel (LN SS) with the cyclic voltammetry technique using indole and thiophene monomers in acetonitrile medium containing lithium perchlorate. The optimization of synthesis parameters such as monomer feed ratio and various scan rates was studied and also their influence on the morphology of the copolymer coatings on LN SS. For the first time, a possible radical cationic electro‐copolymerization mechanism is also proposed in order to understand the electrochemical synthesis. The bonding and structure of the as‐synthesized coatings were characterized using Fourier transform infrared and ¹H NMR spectroscopies. The surface morphology and composition of the coatings were also assessed using scanning electron microscopy and energy‐dispersive X‐ray analysis. It was observed that changes in morphology occurred which had a marked and significant effect on the electrochemical behaviour of the coated LN SS confirmed using electrochemical techniques of potentiodynamic polarization and electrochemical impedance spectroscopy in aqueous 0.5 mol L^?1 H₂SO₄ solution. The obtained results revealed that the copolymer coatings on LN SS provided significant corrosion protection in the acid medium. It was also found that a 1:1 ratio of indole to thiophene yielded the most stable and corrosion‐protective copolymer coating. © 2013 Society of Chemical Industry     

Synthesis and characterization of poly(aniline) and poly(o-anisidine) films in sulphamic acid solution and their anticorrosion properties

Poly(o-anisidine) (POA) and polyaniline (PANI) coatings were synthesized on platinum (Pt) surface and stainless steel (SS) in monomer containing 0.50 M sulphamic acid (SA) solution by means of cyclic voltammetry (CV) technique. Meanwhile, poly(o-anisidine) film was also deposited with a different scan rate on SS electrode. The behaviour of PANI and POA films obtained on stainless steel examined by CV was different from the one obtained for PANI and POA on Pt electrode. The corrosion performances of PANI and POA coatings in 3.5% NaCl solution were investigated with anodic polarization technique and electrochemical impedance spectroscopy (EIS). EIS measurements verified the effect of monomers and that of scan rate on corrosion inhibition of coatings on SS electrode. The results showed that POA film synthesized at low scan rate exhibited an effective anticorrosive property on SS electrode. POA synthesized at low scan rate and PANI coatings provided a remarkable anodic protection to SS substrate for longer exposure time than the one observed for POA coating produced at high scan rate as well as that of bare SS electrode.     

Characterization and anticorrosive properties of poly(2,3‐dimethylaniline)/TiO2 composite synthesized by emulsion polymerization

Poly(2,3‐dimethylaniline)/TiO₂ composite (PTC) was prepared by emulsion polymerization using dodecyl benzene sulfonic acid as emulsifier and dopant. The structure of PTC was characterized by Fourier transformation infrared spectroscopy, wide‐angle X‐ray diffraction, and field emission scanning electron microscopy. Effect of TiO₂ content on the PTC properties was studied by tafel polarization curves, electrochemical impedance spectroscopy, polymerization yield, and cyclic voltammetry measurements. The results showed that the anticorrosion property and electrochemical activity of PTC reached a maximum level when the content of TiO₂ was 15%. Epoxy coatings containing poly(2,3‐dimethylaniline) (P(2,3‐DMA)) and PTC, respectively, were painted on steel and accelerated electrochemical corrosion tests were performed to evaluate the anticorrosion property of the coatings in 3.5% NaCl solution. The results showed that the PTC coating had higher corrosion resistance than that of P(2,3‐DMA). POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Corrosion protective bi‐layered composites of polyaniline and poly(o‐anisidine) on low carbon steel

Bi‐layered composites of polyaniline (PANI) and poly(o‐anisidine) (POA) were investigated for corrosion protection of low carbon steel (LCS). In this work, homopolymers and bi‐layers of PANI and POA were electropolymerized on LCS from an aqueous salicylate solution by using cyclic voltammetry. These coatings were characterized by cyclic voltammetry, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). Corrosion tests were carried out in aqueous 3% NaCl solution for LCS coated with PANI, POA, bi‐layered POA/PANI (POA on top of the PANI) or PANI/POA (PANI on top of the POA) composites using open circuit potential (OCP) measurements, potentiodynamic polarization technique, and electrochemical impedance spectroscopy (EIS). The single layer of PANI and POA protected the LCS in 3% NaCl for 8 and 16 h, respectively. The bi‐layered composite coatings provide effective protection to LCS for a longer time than a single layered PANI or POA coating. However, the corrosion protection offered to LCS depends on the deposition order of polymer layers in the composite. The PANI/POA composite provides better protection to LCS against corrosion than POA/PANI coating. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nonlinear optical properties of poly‐ortho‐toluidine films implantated by N+ ions with different energy

This article reports experimental work on the effect of N⁺ ion implantation on third‐order nonlinear optical properties of POT films. Using K₂Cr₂O₇ as oxidizing agent, poly‐ortho‐toluidine (POT) was synthesized in 1 M hydrochloric. The POT films were prepared by spin‐coating method and then implantated by N⁺ ions (15–30 KeV) at a dose 1.9 × 10¹⁶ ions/cm². The films were characterized by FT‐IR spectroscopy, visible spectroscopy and SEM, their third‐order nonlinear optical susceptibility (χ⁽³⁾) were also examined by a degenerate four‐wave mixing (DFWM) system at 532nm. Compared to pristine POT films, the optical band gap obtained from visible spectra decreased from 3.58 to 3.48 eV when the energy was 30 KeV. Also, The χ⁽³⁾ value of implantated POT films increased from 3.31 × 10⁻¹⁰ esu to 4.04 × 10⁻⁹ esu when the implantated energy was 25 KeV. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

A comparative study on the electrochemical properties of ring‐substituted polyanilines

The redox behavior of polyanilines with ring‐substituted groups synthesized by chemical polymerization, poly‐2,5‐dimethoxyaniline (PDMAn), poly‐m‐chloroaniline (PmClAn) and poly‐o‐toluidine (POT), was studied and the morphology and crystal orientation of platinum particles deposited on these polymer membranes was compared. The oxidation of isopropanol on platinized polyaniline‐modified electrodes as a model reaction was also investigated to examine the electrocatalytic properties of the polymers. The results show that the first oxidation potential of the polymers increases in the following sequence: PDMAn, POT and then PmClAn, which can be explained in terms of the electronic and steric effects of ring‐substituted groups. The growth of Pt particles electrodeposited on doping‐state POT and PDMAn polymer membranes takes place by a ‘progressive nucleation mechanism’, but by an ‘instantaneous nucleation mechanism’ on PmClAn. Platinum crystallites trend towards preferred‐orientation and Pt (200) is the preferred face, but the degree of preferred orientation depends on the polymer. The oxidation potentials of isopropanol are located near 0.3 V, and the oxidation currents increase on platinized polymer‐modified electrodes, indicating that the interaction of polymer with Pt particles might improve the catalytic activity of Pt. Polyanilines act not only as dispersion media but also change the electronic properties of Pt crystalline grains. Copyright © 2005 Society of Chemical Industry     

Inhibition of steel corrosion by electrosynthesized poly(o-anisidine)-dodecylbenzenesulfonate coatings

Poly(o-anisidine)-dodecylbenzenesulfonate (POA-DBSA) coatings were synthesized on stainless steel from aqueous solution containing o-anisidine and dodecylbenzene sulfonic acid by using cyclic voltammetry. These coatings were characterized by Fourier transform infrared spectroscopy (FTIR), UV-vis absorption spectroscopy, scanning electron microscopy (SEM) and cyclic voltammetry (CV). Corrosion tests of these coatings were carried out in aqueous 3% NaCl solution by using open circuit potential (OCP) measurements, potentiodynamic polarization technique, cyclic potentiodynamic polarization measurements and electrochemical impedance spectroscopy (EIS). The results reveal that POA-DBSA acts as a corrosion protective coating on steel and reduces the corrosion rate (CR) of steel almost by a factor of 14.5.     

Preparation of Poly(<Emphasis Type="Italic">o</Emphasis>-toluidine)/Nano Zirconium Dioxide (ZrO<Subscript>2</Subscript>)/Epoxy Composite Coating and Its Corrosion Resistance

Conducting polymers represent a promising application prospect in the field of metal corrosion control. In this investigation, poly(o-toluidine) (POT)/nano zirconium dioxide (ZrO₂) composite were prepared by in situ polymerization of o-toluidine monomer in the presence of nano ZrO₂ particles. Fourier transformation infrared spectroscopy, UV–visible spectroscopy, X-ray diffraction and Scanning electron microscopy were used to characterize the composition and the structure of the composite. POT/nano ZrO₂ composite was mixed with epoxy resin (EP) through a solution blending method and the three components POT/nano ZrO₂/epoxy composite coating was coated onto the surface of steel coupon, and its corrosion protective efficiency was studied by electrochemical measurements and immersion test in 3.5 % NaCl solution as corrosion environment and also compared with that of POT/epoxy composite coated steel, polyaniline (PANI)/epoxy composite coated steel and pure epoxy coated steel. According to the results, POT/nano ZrO₂/epoxy composite coated steel has got higher corrosion resistance than that of POT/epoxy composite coated steel and PANI/epoxy composite coated steel. It was found that POT powders dispersed in the epoxy and polyamide system improved the barrier and electrochemical protection properties of epoxy coating and the addition of nano ZrO₂ particles increased the tortuosity of the diffusion pathway of corrosion substances.     

Actual air separation through poly(aniline‐co‐toluidine)/ethylcellulose blend thin‐film composite membranes

Several multilayer thin‐film composite membranes were fabricated of ethylcellulose (EC) and poly(aniline‐co‐ortho‐toluidine) or poly(ortho‐toluidine) blend as selective thin films and three ultrafiltration membranes with a 10‐ to 45‐nm pore size and 100‐ to 200‐μm thickness as porous supports. The relationships between the actual air‐separation performance through the composite membranes and layer number, composition, casting solution concentration of the thin selective film are discussed. The oxygen‐enriched air (OEA) flux through the composite membranes increases steadily with increasing operational temperature and pressure. The oxygen concentration enriched by the composite membranes appears to decrease with operating temperature, but increases with operating pressure. The actual air‐separation property through the composite membranes seems to remain nearly constant for at least 320 days. The respective highest OEA flux, oxygen flux, and oxygen concentration, respectively, were found to be 4.78 × 10⁻⁵ cm³ (STP)/s · cm², 2.2 × 10⁻⁵ cm³ (STP)/s · cm², and 46% across EC/poly(o‐toluidine) (80/20) blend monolayer thin‐film composite membranes in a single step at 20°C and 650 kPa operating pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 458–463, 2000     

Composites of poly(2‐chloroaniline) and poly(o‐toluidine) with pumice and their application in the removal of chromium(VI) ions from aqueous solutions

Poly(2‐chloroaniline) (P2ClAn)/pumice (Pmc) and poly(o‐toluidine) (POT)/Pmc composites were synthesized via the chemical oxidative polymerization of 2‐chloroaniline and o‐toluidine in the presence of a dispersion of Pmc powders in water solvent with an (NH₄)₂S₂O₈ oxidant. The composites were characterized with Fourier transform infrared (FTIR) spectroscopy, thermo‐gravimetric/differential thermal analysis (TG‐DTA), and scanning electron microscopy devices. The presence of P2ClAn and POT in the structure of the composites was confirmed by FTIR. Theresults of analysis show strong interactions between the homopolymers and Pmc. The applicability of the P2ClAn/Pmc and POT/Pmc composites were investigated for the removal of Cr(VI) ions in water. Batch adsorption experiments were carried out as a function of pH, initial concentration, time, adsorbent dosage, and temperature. The batch sorption kinetics were tested, and the applicability of the Langmuir and Freundlich adsorption isotherms for this system was tested at 20 ± 1°C. An initial pH of 3.0 was most favorable for Cr(VI) removal by all adsorbents. The adsorption capacities obtained were 0.187 and 4.959 mmol/g of adsorbent for POT/Pmc and P2ClAn/Pmc from the Freundlich and Langmuir adsorption isotherms, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis of poly(o‐toluidine) in the presence of magnetic field and dysprosium chloride

The poly‐o‐toluidine (POT) was prepared under different magnetization in solution containing 0.5 mol dm^?3o‐toluidine, 1.0 mol dm^?3 HCl with and without 0.5 mol dm^?3 DyCl₃, respectively. Their conductivity, UV–vis, FTIR spectra, X‐ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscope (SEM) were investigated. The results of conductivity showed that magnetic field and the cooperative effect of Dy³⁺ and magnetic field do obvious effect to conductivity of POT. Meantime, they also can make the energy for the π–π* transitions and quinoid ring transition in UV–vis spectra smaller. At high magnetization the peaks of POT due to Q? NH⁺? B or B? NH⁺? B and C? H out of plane on 1,4‐ring or 1,2,4‐ring disappeared in FTIR spectra. Magnetic field and Dy³⁺ can make three dimensions morphologies of the POT clear, but they scarcely affect the crystallinity of POT. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2174–2179, 2007     

Evaluation of Ni‐Mo and Ni‐Mo‐P Electroplated Coatings on Stainless Steel for PEM Fuel Cells Bipolar Plates

Stainless steel bipolar plates (BPPs) are the preferred choice for proton exchange membrane fuel cells (PEMFCs); however, a surface coating is needed to minimize contact resistance and corrosion. In this paper, Ni–Mo and Ni–Mo–P coatings were electroplated on stainless steel BPPs and investigated by XRD, SEM/EDX, AFM and contact angle measurements. The performance of the BPPs was studied by corrosion and conduction tests and by measuring their interfacial contact resistances (ICRs) ex situ in a PEMFC set‐up at varying clamping pressure, applied current and temperature. The results revealed that the applied coatings significantly reduce the ICR and corrosion rate of stainless steel BPP. All the coatings presented stable performance and the coatings electroplated at 100 mA cm⁻² showed even lower ICR than graphite. The excellent properties of the coatings compared to native oxide film of the bare stainless steel are due to their higher contact angle, crystallinity and roughness, improving hydrophobicity and electrical conductivity. Hence, the electroplated coatings investigated in this study have promising properties for stainless steel BPPs and are potentially good alternatives for the graphite BPP in PEMFC.     

不同材料表面镍-磷-锌盐纳米复合化学镀层性质的比较

研究比较了D310硅钢片和A3钢片表面Ni-P-Zn3(PO4)2,Ni-P-ZnSnO3和Ni-P-ZnSiO3纳米复合化学镀层的外貌和性质。用扫描电子显微镜（SEM）观察外貌：称重法测定厚度,通过10％NaCl溶液,1％H2S气体加速腐蚀试验,10％,CuSO4溶液点滴试验,饱和KCl溶液循环伏安（CV）试验,抗粘性试验及抗高温氧化试验等多种手段测定其性能。结果表明：纳米复合化学镀层的性能优于镍－磷镀层和其它微米复合镀层。     

Electropolymerization of sulfonated phenol by cyclic voltammetry

In this work, electropolymerization of sulfonated phenol were performed by cyclic voltammetry (CV) on planar or nano‐architecture substrates. The corresponding CV curves were analyzed and compared. The obtained polymer was characterized by SEM, EDX, and FTIR. The results suggested that it was feasible to electropolymerize sulfonated phenol on different substrates. The facility of electropolymerization on different substrates was as follows: graphite carbon > stainless steel plate > ZrO₂ nanotube. The peak current density of CV curve on stainless steel kept constant from the second cycle possibly attributed to the promoting effects of sulfonic acid groups: improving the ionic conductivity, changing the packing mode of polymer chains, and enhancing the permeability of the film to monomers. This work offered some insights into electrochemical synthesis of proton‐conducting membrane for varied special applications, such as micro‐sized fuel cell, sensor, battery, and other solid‐state ionic devices. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013