Electrochemical synthesis and corrosion performance of poly(pyrrole-co-o-anisidine)

The electrochemical synthesis of poly(o-anisidine) homopolymer and its copolymerization with pyrrole have been investigated on mild steel. The copolymer films have been synthesized from aqueous oxalic acid solutions containing different ratios of monomer concentrations: pyrrole:o-anisidine, 9:1, 8:2, 6:4, 1:1. The characterization of polymer films were achieved with FT-IR, UV–visible spectroscopy and cyclic voltammetry techniques. The electrochemical synthesis of homogeneous-stable poly(o-anisidine) film with desired thickness was very difficult on steel surface. Therefore its copolymer with pyrrole has been studied to obtain a polymer film, which could be synthesized easily and posses the good physical–chemical properties of anisidine. The kinetics and rate of copolymer film growth were strongly related to monomer feed ratio. The introduction of pyrrole unit into synthesis solution increased the rate of polymerization and the substrate surface became covered with polymer film soon, while this process required longer periods in single o-anisidine containing solution. The protective behavior of coatings has been investigated against steel corrosion in 3.5% NaCl solution. For this aim electrochemical impedance spectroscopy (EIS) and anodic polarization curves were utilized. The synthesized poly(o-anisidine) coating exhibited significant protection efficiency against mild steel corrosion. It was shown that 6:4 ratio of pyrrole and anisidine solution gave the most stable and corrosion protective copolymer coating.     

Potentiodynamic deposition of poly (o-anisidine-co-metanilic acid) on mild steel and its application as corrosion inhibitor

For the first time, poly (o-anisidine-co-metanilic acid) (PASM) was deposited on mild steel substrate by electrochemical polymerization of o-anisidine and metanilic acid monomers in aqueous solution of 0.1 M H₂SO₄. The electrochemical polymerization of o-anisidine takes place in the presence of metanilic acid monomer and uniform, strongly adherent coating was obtained on the substrate. The electroactivity of copolymer was studied by cyclic voltammetry and AC impedance techniques. There is an increasing anodic current due to oxidation of metanilic acid monomer at the surface of the electrode when the applied potential is cycled from −0.2 V to 0.8 V. These deposits were characterized by Fourier transform infrared (FTIR) spectroscopy, UV-vis and TG/DTA techniques. The effect of various concentrations of PASM copolymer solution in acid rain corrosive media has been studied through potentiodynamic polarization, AC impedance and I-E curve methods. The soluble form of polymeric solution provided better anti-corrosive behavior in artificial acid rain solution.     

Corrosion protection aspects of electrochemically synthesized poly(o-anisidine-co-o-toluidine) coatings on copper

The poly(o-anisidine-co-o-toluidine) coatings were synthesized on copper substrates by electrochemical copolymerization of o-anisidine with o-toluidine using sodium salicylate as supporting electrolyte. These coatings were characterized by cyclic voltammetry, UV-vis absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and scanning electron microscopy (SEM). The formation of the copolymer with the mixture of monomers in the aqueous sodium salicylate solution was ascertained by a critical comparison of the results obtained with the polymerization of the individual monomers, o-anisidine and o-toluidine, respectively. The corrosion protection aspects of poly(o-anisidine-co-o-toluidine) coatings to copper was investigated in aqueous 3% NaCl solution by potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results of the potentiodynamic polarization measurements and EIS studies showed that the poly(o-anisidine-co-o-toluidine) coatings provided the effective corrosion protection to copper than that of respective homopolymers. The corrosion rate is observed to depend on the feed ratio of o-toluidine used for the synthesis of the copolymer coatings.     

Novel approaches to developing carbon nanotube based polymer composites: fundamental studies and nanotech applications

The adsorption of several types of conducting polymers on carbon nanotubes is investigated by electrical transport measurements. We report the optoelectronic properties occurring in single-walled carbon nanotubes (SWNTs) conjugated polymer, poly(3-octylthiophene), composites. Al/polymer-nanotube composite/indium-tin oxide diodes show photovoltaic behavior proposing that the main reason for this increase is the photoinduced electron transfer at the polymer/nanotube interface. Interesting results were obtained in the case of poly(o-anisidine) (POAS)-multi-walled nanotubes (MWNTs) composites where the increment of monolayers results in a significant improvement of the specific conductivity. POAS-coated MWNTs thin films demonstrated their potentiality as a new class of materials for inorganic vapors detection for environmental applications.     

Protective properties of polyaniline and poly(aniline-co-o-anisidine) films electrosynthesized on brass

Polyaniline and poly(aniline-co-o-anisidine) films were deposited on brass (Cu40Zn). The synthesis processes of homo and copolymer film were carried out under cyclic voltammetric condition from 0.12 M aniline and 0.06 M aniline + 0.06 M o-anisidine containing 0.2 M sodium oxalate solutions. Homo and copolymer films were characterized by scanning electron microscopy (SEM). SEM images clearly show that one of the brass electrodes was covered with a black copolymer film of strongly adherent homogeneous characteristic while the other one with a porous dark green homo polymer one. The corrosion performances of coated and uncoated electrodes in 3.5% NaCl were evaluated with the help of AC impedance spectroscopy, anodic polarization plots and open circuit potential–time curves. The protective effect of homo and copolymer films formed on brass grew in parallel with extended exposure time. It was only observed with copolymer-coated electrode that changes in the charge transfer resistance of copolymer-coated electrode were related to strong adsorption of copolymer film on the brass surface which led to the formation of a protective oxide layer due to its catalytic behaviour.     

Synthesis and characterization of polypropylene-based polymer hybrids linking poly(methyl methacrylate) and poly(2-hydroxyethyl methacrylate)

Isotactic polypropylene-based polymer hybrids linking poly(methyl methacrylate) (PMMA) and poly(2-hydroxyethyl methacrylate) (PHEMA) were successfully synthesized by a graft copolymerization from maleic anhydride-modified polypropylene (PP-MAH). PP-MAH reacted with ethanolamine to produce a hydroxyl group containing polypropylene (PP-OH) and the thus obtained PP-OH was treated with 2-bromoisobutyryl bromide and converted to a 2-bromoisobutyryl group containing polypropylene (PP-Br). The metal-catalyzed radical polymerization of MMA with PP-Br was performed using a copper catalyst system in o-xylene solution at 100 °C to give the PP-based polymer hybrids linking PMMA segments (PP-PMMA hybrids). Thus obtained PP-PMMA hybrids demonstrated higher melting temperature than PP-Br and microphase-separation morphology at the nanometer level owing to the chemical linkage between both segments. On the other hand, the polymer hybrids linking PHEMA segment (PP-PHEMA hybrids) were also obtained by the radical polymerization of HEMA with PP-Br in o-xylene slurry at 25 °C. TEM observation suggested that the polymerization mainly initiated on the surface of the PP-Br powder, led to the peculiar core-shell-like morphology. These PP-PHEMA hybrid powders showed a good affinity with water due to the hydrophilicity of the PHEMA segments.     

Newer dynamic electrochromic nanorods of poly(o-anisidine-co-ethyl 4-aminobenzoate) synthesized by electrochemical polymerization

Electrochemical copolymerization of o-anisidine with ethyl 4-aminobenzoate was carried out in aqueous 0.1 M HClO₄ by employing cyclic voltammetry. Copolymer films were grown for different molar concentration ratios of ethyl 4-aminobenzoate. Electrochemical homopolymerizations of o-anisidine and ethyl 4-aminobenzoate were carried out independently under similar conditions. The copolymers exhibited high solubility in many polar solvents. The scan rate exerted good influence on the polymer effect on this glassy carbon electrode copolymer film, revealing electroactive film's excellent adherent properties. Spectroelectrochemical studies of the copolymer film were carried out on indium tin oxide plates. The copolymer was characterized by FTIR spectral data. The surface morphology was studied using SEM and TEM analysis. The electrical conductivity of copolymer was measured by four-probe conductivity meter.     

Characterization of ultrathin electroactive films synthesized via the self-limiting electropolymerization of o-methoxyaniline

The electropolymerization of o-methoxyaniline under self-limiting deposition conditions yields ultrathin (<20 nm) coatings of an insoluble, low-molecular-weight polymer on planar indium-tin-oxide electrode substrates. The self-limiting nature of the electropolymerization is achieved by using citrate-buffered aqueous electrolytes (pH 4.7) in which the developing polymer that deposits at the electrified interface is neither conductive nor permeable to monomer. Although non-conductive as electrodeposited, the resulting poly(o-methoxyaniline) coating becomes electroactive when transferred to acidic aqueous electrolytes. The morphology and chemical structure of the poly(o-methoxyaniline) coatings are characterized by surface-sensitive methods including atomic force microscopy, specular-reflectance infrared spectroscopy, X-ray photoelectron spectroscopy, and electrochemistry. Fundamental understanding of the structure/property relationships derived from these investigations on planar substrates will ultimately be applied to three-dimensional electrode nanoarchitectures that incorporate such electroactive coatings for enhanced charge-storage functionality.     

Characterization of substituted polyaniline films using Raman spectroscopy: III. Study of a methoxylated polymer: POMA

The electropolymerization of o-anisidine leads to the formation of a polymer which is in the same time strongly oxidized and charged in a large potential range: the poly-o-methoxyaniline (POMA). The POMA Raman features are strongly different from the polyaniline (PANI) ones; in particular a new band, absent from the PANI spectrum, prevails in a large potential range. The nature of the polymer structures obtained in function of the polarization potential is discussed from their Raman spectra. A new polymeric configuration of the oxidized/charged rings is therefore described.     

Finely dispersed Pt nanoparticles in conducting poly(o-anisidine) nanofibrillar matrix as electrocatalytic material

A new approach based on stepwise oxidation of o-anisidine is explored for generating nanoporous films of poly(o-anisidine), POA and loading of Pt nanoparticles that are subsequently used for electrocatalysis of methanol oxidation are presented and compared with bulk Pt. POA film can easily be prepared by stepwise electro-oxidation procedure with very high porosity consisting of nanofibrillar structure using without templates. Controlled sizes of Pt nanoparticles were entrapped into POA matrix by a two-step process in which first PtCl₆²⁻ ions are sorbed into the pores of polymer matrix followed by electroreduction at −0.55 V in a 0.5 M H₂SO₄ solution. Loading of Pt nanoparticles (10-200 μg/cm²) onto POA matrix were accomplished by varying the concentration (2-10 mM) of the sorbate, i.e., H₂PtCl₆. The sizes of the Pt nanoparticles were determined from TEM analysis and Pt particles were found to be in the range of 10-20 nm. The crystallite phase of Pt particles in POA was examined from XRD pattern. AFM image further supports Pt particles embedded in POA matrix.     

Electrochemical and in situ TM-AFM studies of the polymerization conditions on poly(o-methoxyaniline) film morphology

The in situ atomic force microscopy and the electrochemical studies on electropolymerization of the o-methoxyaniline in the 0.0-0.8 V versus NHE range of the electrode potential are described. It is proved that in the 0.0-0.3 V versus NHE a redox process takes place, resulting in the formation of poly(o-methoxyaniline) in its reduced form, leucoemeraldine. The different morphologies are exhibited by poly(o-methoxyaniline) under different polymerization conditions. The microscopic results show that with the increase of the monomer concentration in the bulk of electrolyte solution the globular morphology, related to the coil like molecular structure, is replaced by the fibrilar one, related to the opened-up, more conductive extended coil structure. It is shown that oxidation of a leucoemeraldine state of polymer to its emeraldine state results in the change of the morphology from the chain like structure to the massive fibrilar like structure. The reduction of oxidized polymer results in its irreversible fragmentation.     

Preparation and solubility of a partial ladder copolymer from p-phenylenediamine and o-phenetidine

A series of copolymers were synthesized by chemically oxidative polymerization of p-phenylenediamine (PPD) and o-phenetidine (PHT) in acidic aqueous media. The polymerization yield, intrinsic viscosity, and solubility of the copolymers were comprehensively studied by changing the comonomer ratio, polymerization time and temperature, oxidant, monomer/oxidant ratio, and acidic medium. As-prepared fine powder of the PPD/PHT copolymers was characterized by FT-IR, UV-vis, high-resolution ¹H-NMR, and DSC techniques. A circular dichroism technique was firstly used to characterize the macromolecular structure of the copolymers. The results showed that the oxidative copolymerization from PPD and PHT is exothermic and the resulting copolymers exhibit an enhanced solubility in most of the organic solvents as compared with poly(p-phenylenediamine), sometimes also with poly(o-phenetidine). The polymer obtained is a real copolymer containing PPD and PHT units, and the actual PPD/PHT ratio calculated by ¹H-NMR spectra of the polymers is very close to the feed ratio. The DSC measurement indicates that the copolymers are amorphous and chemically instable at elevated temperature.     

Epitaxial synthesis of poly(p-xylylene)

When poly(p-xylylene) is synthesized from gaseous monomers, it grows epitaxially on substrates. The effects of the substrate and annealing on the epitaxy are examined by growing the polymer on cleavage (001) surfaces of four kinds of alkali halides (NaCl, KCl, KBr and Kl). The polymer crystallizes with its chains oriented along the 〈100〉 and 〈010〉 directions of the substrates and the faster growth planes are parallel to the (001) plane of substrate, i.e., the (010) plane of the α-form crystal and the (100) plane of the β-form. The degree of orientation is the highest on KBr and the lowest on NaCl. The lattice matching requirement is important in the epitaxial synthesis. The observed orientation of the polymer chain on each substrate is compared with the orientation expected from a minimum of interfacial potential energy calculated on the basis of dispersion-repulsive forces between atoms in the polymer and ions in the substrate. The orientational angle of polymer chain on the substrates and the degree of its orientation are qualitatively explained in terms of the processes of monomer deposition, polymerization and crystallization under the directive influence of the substrate.     

Synthesis and characterization of conducting copolymers from aniline and o‐anisidine in HCl solutions

Conducting poly(aniline‐co‐o‐anisidine) (PAS) films with different ratios of aniline units in the polymer chain were prepared by oxidative polymerization of different molar ratios of aniline and o‐anisidine in 1 M HCl using cyclic voltammetry. Due to the much higher reactivity of o‐anisidine, the structure and properties of PASs were found to be dominated by the o‐anisidine units. The polymerization of poly‐o‐anisidine and PASs followed zero‐order kinetics with respect to formation of the polymer (film thickness) and the autocatalytic polymerization of aniline was completely inhibited. In contrast to polyaniline, a decrease in the polymerization temperature was found to increase the amount of copolymer formed and its redox charge. The presence of aniline units in PASs led to a pronounced increase in the molecular weight and conductivity, and a decrease in the solubility in organic solvents. Repetitive charging/discharging cycles showed that PASs resist degradation more than polyaniline. Copyright © 2003 Society of Chemical Industry     

Electrical properties of metal (indium)/polyaniline Schottky devices

Schottky devices were fabricated by thermal evaporation of indium on chemically synthesized polyaniline, poly(o-anisidine), and poly(aniline-co-ortho-anisidine) copolymer. Electrical characterization of each of these devices was carried out using current (I)-voltage (V) and capacitance (C)-voltage (V) measurements. The value of various junction parameters such as rectification ratio, ideality factor, and barrier heights of an In/poly(aniline-co-o-anisidine) Shootky device were found to be 300, 4.41, and .4972 V compared to the values of 60, 5.5, and 0.5101 V obtain for an In/polyaniline device, respectively. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2745–2748, 1997     

Synthesis and Characterization of a Conducting Composite of Polyaniline,Poly(o-Anisidine), and Poly(Aniline-co-o-Anisidine)

A conducting composite of polyaniline, poly(o-anisidine), and poly(aniline-co-o-anisidine) using incorporation of TiO₂ and SiO₂ was prepared by electrochemical polymerization. The films were electropolymerized in a solution containing 0.1 M monomer(s), 1 M sulfuric acid as supporting electrolyte, and 10^?5 M TiO₂ and SiO₂ by applying a sequential linear potential scan rate of 50 mV/s between ? 0.2 and 1.0 V versus an Ag/AgCl electrode. The composites were characterized by cyclic voltametry, UV-visible spectroscopy, electrical conductivity, and thermogravimetric analysis. It was observed that the UV-visible peaks appeared in the region of the conducting emerladine salt phase. In an overall study, the polymers prepared using TiO₂ had a higher conductivity than those prepared with SiO₂; however, higher conductivity was observed for the polyaniline-TiO₂ conducting composite than for the other polymers. The composites did not lose their color at higher temperature and hence can be utilized as the conductive pigments required for antielectrostatic applications.     

3D porous polymeric conductive material prepared using LbL deposition

In this work a 3D porous polymeric conducting material is derived from a multi-percolated polymer blend system. The work has focused on the preparation of low surface area porous substrates from polymer blends followed by the deposition of polyaniline conductive polymer (PANI) on the internal porous surface using a layer-by-layer (LbL) technique. The approach reported here allows for the percolation threshold concentration of polyaniline conductive polymer (PANI) to be reduced to values of no more than 0.19%. Furthermore, depending on the amount of PANI deposited, the conductivity of the porous substrate can be controlled from 10⁻¹⁵ S cm⁻¹ to 10⁻³ S cm⁻¹.Ternary and quaternary multi-percolated systems comprised of high-density polyethylene (HDPE), polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(vinylidene fluoride) (PVDF) are prepared by melt mixing and subsequently annealed in order to obtain large interconnected phases. Selective extraction of PS, PMMA and PVDF result in a fully interconnected porous HDPE substrate of ultra-low surface area and highly uniform sized channels. This provides an ideal substrate for subsequent polyaniline (PANI) addition. Using a layer-by-layer (LbL) approach, alternating poly(styrene sulfonate) (PSS)/PANI layers are deposited on the internal surface of the 3-dimensional porous polymer substrate. The PANI and sodium poly(styrene sulfonate) (PSS) both adopt an inter-diffused network conformation on the surface. The sequential deposition of PSS and PANI has been studied in detail and the mass deposition profile demonstrates oscillatory behavior following a zigzag-type pattern. The presence of salt in the deposition solution results in a more uniform deposition and more thickly deposited PSS/PANI layers. The conductivity of these samples was measured and the conductivity can be controlled from 10⁻¹⁵ S cm⁻¹ to 10⁻⁵ S cm⁻¹ depending on the number of deposited layers. In the case of a porous sample which can be crushed, applying a load to the substrate can be used as an additional control parameter. In that sample a high load results in higher conductivity with values as high as 10⁻³ S cm⁻¹ obtained. The work described above has focused on very low surface area porous substrates in order to generate a conductive device with the lowest possible concentration values of polyaniline, but high surface area substrates can also be readily prepared using this approach.     

Catalytic hydrogenation of o-nitroanisole in a microreactor: Reactor performance and kinetic studies

Hydrogenation of o-nitroanisole to o-anisidine was conducted in a packed-bed microreactor as a model hydrogenation reaction of importance to the pharmaceutical and fine chemicals industries with the aim of investigating the reactor performance and kinetics of the reaction. The effects of different processing conditions viz. hydrogen pressure, o-nitroanisole concentration, temperature, and residence time on the conversion of o-nitroanisole, space-time yield (STY), and selectivity of o-anisidine were studied using 2% Pd/zeolite catalyst. The kinetic study was undertaken in a differential reactor mode keeping the conversion of o-nitroanisole at less than 10%. During the kinetic study, it was observed that the intermediate 2-methoxynitrosobenzene was present in the reactor at low catalyst loading and low conversions because of short residence time in the reactor. Therefore, for the kinetics study, the overall reaction was treated as comprising two separate reactions: first the reduction of o-nitroanisole to 2-methoxynitrosobenzene and then, the reduction of 2-methoxynitrosobenzene to o-anisidine. Internal and external mass and heat transfer limitations in the microreactor were examined. Different rate laws using different mechanisms from the literature were considered to fit the experimental data. Two rate equations for the two consecutive reactions assuming Langmuir-Hinshelwood mechanism provided the best fit to the experimental data. These two rate equations predicted the experimental rates within 10% error. Experiments were also carried out in an integral reactor, and the reactor performance data were found to be in agreement with the predictions of the theoretical models.     

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.     

Epoxy-based anticorrosive coating developed with modified poly(<Emphasis Type="Italic">o</Emphasis>-anisidine) and depolymerized product of PET waste

Poly(o-anisidine) (POA) is used as a modifier in an epoxy system to enhance its anticorrosive properties. The modification of POA is done by aminosilane to introduce amine functionality on the surface. Through this functionality, it becomes part of the coating backbone during curing of an epoxy-polyaminoamide system. The concentration of poly(o-anisidine) has been varied as 1, 3, and 5 wt%. Depolymerized product of polyethylene terephthalate (PET) obtained from aminolysis of PET with ethylamine has amine functionality. Depolymerized product is added at concentrations of only 1 and 3 wt%. The same concentration is used with 5 wt% of silane-modified POA. The synthesized POA and silane-modified POA (Si-POA) have been characterized by FTIR, UV–Visible, and XRD analysis. The coating is characterized by mechanical properties and it is observed that pencil hardness and scratch hardness of the coating were enhanced to 6H and 3.5 kg from 2H and 2.5 kg of a plain epoxy system. The anticorrosive properties of Si-POA are better as compared to plain POA, but the addition of depolymerized product is unable to improve the anticorrosive performance of the coating. In EIS study, it is observed that 5% Si-POA system shows the highest impedance > 10 G (Ω) and it has a tendency to retain anticorrosive performance for longer duration.