Epoxy/polyaniline–ZnO nanorods hybrid nanocomposite coatings: Synthesis,characterization and corrosion protection performance of conducting paints

The objective of this research is the production of an epoxy coating blended with organic–inorganic hybrid nanocomposite as a corrosion inhibiting pigment applied over carbon steel grade ST37. A series of conducting polyaniline (PANI)–ZnO nanocomposites materials has been successfully prepared by an in situ chemical oxidative method of aniline monomers in the presence of ZnO nanorods with camphorsulfonic acid (CSA) and ammonium peroxydisulfate (APS) as surfactant and initiator, respectively. The synthesized polymers were characterized by X-ray diffraction pattern (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and electrical conductivity techniques. Synthesized nanocomposites were solved in tetraethylenpentamine (TEPA), and then prepared solution was mixed with epoxy and then was applied as a protective coating on carbon steel plates. The anti-corrosion behavior of the epoxy binder blended with PANI–ZnO nanocomposites were studied in 3.5% NaCl solution at a temperature of 25 °C by electrochemical techniques including electrochemical impedance spectroscopy (EIS) and chronopotentiometry at open circuit potential (OCP). It was observed that the epoxy coating containing conducting PANI–ZnO nanocomposites exhibited higher corrosion resistance and provided better barrier properties in the paint film in comparison with pure epoxy and epoxy/PANI coatings. In the case of conducting coatings, the OCP was shifted to the noble region due to presence of PANI pigments. Additionally, the possibility of formation of a passive film in the presence of PANI was reinforced at the substrate–coating interface. SEM studies taken from surface of the coatings showed that epoxy/PANI–ZnO hybrid nanocomposite coating systems (EPZ) are crack free, uniform and compact. Furthermore, it was found that the presence of ZnO nanorods beside PANI can significantly improve the barrier and corrosion protection performance of the epoxy coating due to the flaky shaped structure of the PANI–ZnO nanocomposites.     

Investigation of corrosion protection performance of epoxy coatings modified by polyaniline/clay nanocomposites on steel surfaces

In this study, polyaniline (PANI) and polyaniline/clay nanocomposites were prepared via in situ oxidative polymerization. The morphology of nanocomposites structures was investigated by X-ray diffraction (XRD). The chemical structures of PANI and PANI/clay nanocomposites were examined via Fourier transform infrared (FT-IR) spectroscopy. Polyaniline-based pigments were introduced into epoxy paint and applied on steel substrates. The effect of clay addition and the type of clay cation, including Na⁺ in natural clay (MMT) and alkyl ammonium ions in organo-modified montmorillonite (OMMT), on the anticorrosion performance of epoxy-based coatings was investigated through electrochemical Tafel test, electrochemical impedance spectroscopy and immersion measurements in NaCl solution. The stability of the adhesion of the neat and modified epoxy coatings to the steel surface was also examined. The results indicated that introduction of PANI/OMMT nanocomposite into epoxy paint results in improved anticorrosion properties in comparison with PANI/MMT and neat PANI.     

Synthesis and characterization of polyaniline nanorods as curing agent and nanofiller for epoxy matrix composite

Novel PANI nanorods with average diameter of 21-53 nm and length of 0.5-1 μm were synthesized by dispersion polymerization method. The morphology of obtained PANI nanorods was significantly dependent on the type of salt, stirring, and polymerization temperature. Dispersion polymerization with FeCl₃ produced longer nanorods than ammonium persulfate (APS) and magnetic stirring decreased the length of nanorods. While the average diameter of PANI nanorods decreased with increasing reaction temperature, the electrical conductivity dropped considerable at high polymerization temperature due to the increment of insulating emeraldine base. Dynamic differential scanning calorimetry (DSC) study showed that the heat of cure was independent of heating rate. On the contrary, the heat of cure was proportional to the content of PANI nanorods as a role of curing agent. Isothermal DSC study revealed that the cure behavior of LCE/PANI nanorod system was an auto-catalyzed reaction. Thermogravimetric analysis (TGA) indicated that the thermal stability of cured LCE/PANI nanocomposite was significantly dependent on the PANI nanorod composition. In addition, the electrical conductivity of LCE/PANI nanocomposite materials was higher than that of conventional epoxy composites. Therefore, PANI nanorods played a role of curing agent owing to the existent amine group and acted as reinforcing filler for cured LCE nanocomposites.     

Anti-corrosive properties of Poly(aniline-co-2,3-xylidine)/ZnO nanocomposite coating on low-carbon steel

A copolymer nanocomposite Poly(aniline-co-2,3-xylidine)/ZnO [Poly(AN-co-XY)/ZnO], pure copolymer and its homopolymers namely, Poly(aniline-co-2,3-xylidine) [Poly(AN-co-XY)], Polyaniline (PANi) and Poly (2,3-xylidine) were synthesized by chemical oxidative polymerization using ammonium persulfate as an oxidant in hydrochloric acid medium. The synthesized compounds were characterized by FTIR, XRD, SEM, and TEM techniques. Saturated solutions of the synthesized compounds were made in N-methyl-2-pyrrolidone and casted on low-carbon steel specimens using 10% epoxy resin as a binder. The anticorrosion behavior of polymeric coatings was studied in 3.5 wt% NaCl solution at a temperature of 30 °C by electrochemical techniques, which include: open-circuit potential, potentiodynamic polarization and electrochemical impedance spectroscopy. Protective properties of nanocomposite coating were also evaluated at different immersion times for an extended period of 60 days. Anticorrosion properties of nanocomposite coating were compared with parent copolymer and individual homoplymers. SEM photomicrographs of the coated surface showed that Poly(AN-co-XY)/ZnO nanocomposite coating is crack free, uniform, and compact, whereas, copolymer and homopolymer coatings have surface defects. The performance of the polymer coatings followed the order: Poly(AN-co-XY)/ZnO > Poly(AN-co-XY) > PANi > Poly(2,3-xylidine). The presence of ZnO nanoparticles in copolymer resulted in significant improvement in corrosion resistance and provided better barrier properties.     

Intercalated polyaniline–kaolinite nanocomposite prepared via in situ mechanochemical synthesis

The in situ polymerization of aniline monomers within kaolinite interlayers easily led to an intercalated polyaniline (PANI)–kaolinite nanocomposite through a facile mechanochemical method. The X‐ray diffraction results demonstrate that PANI was successfully intercalated in the interlayers of kaolinite, which was lightened by an increased basal spacing from 7.24 to 14.67 Å of kaolinite in the as‐synthesized nanocomposite, and the characterization results from Fourier transform infrared spectrometry, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy further confirm this conclusion. The thermal stability of PANI was improved significantly when PANI was intercalated into kaolinite to form the nanocomposite; this was proven by thermogravimetric analysis. Moreover, a panel experiment was carried out under a simulated marine environment to evaluate the anticorrosive effect of the as‐prepared product, and the results show that the epoxy resin/intercalated PANI–kaolinite nanocomposite coating had a better anticorrosive effect than that of the neat epoxy resin coating. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43551.     

Electrically conductive composites based on epoxy resin containing polyaniline–DBSA‐ and polyaniline–DBSA‐coated glass fibers

Four kinds of polyaniline (PANI)‐coated glass fibers (GF–PANI) combined with bulk PANI particles were synthesized. GF–PANI fillers containing different PANI contents were incorporated into an epoxy–anhydride system. The best conductivity behavior of the epoxy/GF–PANI composites was obtained with a GF–PANI filler containing 80% PANI. Such a composite shows the lowest percolation threshold at about 20% GF–PANI or 16% PANI (glass fiber‐free basis). The PANI‐coated glass fibers act as conductive bridges, interconnecting PANI particles in the epoxy matrix, thus contributing to the improvement of the conductivity of the composite and the lower percolation threshold, compared with that of a epoxy/PANI–powder composite. Particularly, the presence of glass fibers significantly improves the mechanical properties, for example, the modulus and strength of the conductive epoxy composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1329–1334, 2004     

Preparation of PANI/epoxy/Zn nanocomposite using Zn nanoparticles and epoxy resin as additives and investigation of its corrosion protection behavior on iron

Conducting polyaniline, zinc and epoxy resin solely have anticorrosive properties by different mechanisms on metallic substrates. In this work the triple hybrid of PANI/epoxy/Zn nanocomposite was prepared as a thin layer coating (70 ± 5 μm) on iron coupons and its anticorrosion performance was investigated in HCl (0.1 M) as corrosive solution. Epoxy resin and zinc nanoparticles were applied as additives in the PANI matrix to improve the mechanical properties of PANI coating and investigate their synergetic effects on the anticorrosion performance of PANI coating. At first PANI/Zn nanocomposite coatings with different Zn contents were prepared and the zinc content optimized so that the coating achieve the best anticorrosion performance. Accordingly the iron coupons coated by PANI/Zn coating having 4 wt% Zn content showed more noble open circuit potential and lower corrosion current values. Then epoxy resin was applied as additive to the optimized formulation of PANI/Zn coating in different weight percents (0–20 wt%) and the anticorrosion performance of the related PANI/epoxy/Zn triple hybrid nanocomposite coatings was evaluated. Results showed that the addition of epoxy resin causes to the decreasing of corrosion current of iron samples coated by PANI/epoxy/Zn nanocomposite. An optimum range of 3–7 wt% was obtained for the epoxy content in the composition of PANI/epoxy/Zn nanocomposite in which the coating exhibits the best anticorrosion performance. Iron metal coupon was elementally analyzed and the PANI/Zn and PANI/epoxy/Zn nanocomposites were characterized using Fourier Transform Infrared spectroscopy, X-ray diffraction patterns and Scanning Electron Microscopy techniques.     

Facile preparation of conductive paint made with polyaniline/dodecylbenzenesulfonic acid dispersion and poly(methyl methacrylate)

We investigated an easy way to prepare industrially a conductive paint made with polyaniline (PANI)/dodecylbenzenesulfonic acid (DBSA) dispersion and poly(methyl methacrylate) (PMMA) in organic media. First, water‐dispersible PANI doped with DBSA was chemically synthesized with aniline sulfate using ammonium persulfate in water, and the resulting PANI/DBSA was readily extracted from the reaction medium with a mixture of toluene and methyl ethyl ketone (MEK) (toluene:MEK = 1:1 (v/v)), which is useful for industrial applications. The obtained PANI/DBSA organic dispersion was mixed with PMMA organic solution to give the corresponding PANI/DBSA conductive paint containing PMMA. A film prepared with the resulting PANI/DBSA conductive paint was found to possess relatively good conductivity and low surface resistivity for a conductive paint utilized for an electrostatic discharge even at low PANI/DBSA content in the PANI/DBSA–PMMA composite film (the conductivity and the surface resistivity were 9.48 × 10^?4 S cm^?1 and 3.14 × 10⁶ Ω cm^?2, respectively, when the feed ratio of PANI/DBSA:PMMA was 1:39 (w/w)). Furthermore, it was found that the conductivity of the film composed of PANI/DBSA–PMMA composite can be readily and widely controlled by the PANI/DBSA content of the composite or by the amount of DBSA used during the PANI/DBSA synthesis. The highest conductivity of PANI/DBSA–PMMA composite film (7.84 × 10^?1 S cm^?1) was obtained when the feed ratio of PANI/DBSA:PMMA was 1:4 (w/w). Copyright © 2007 Society of Chemical Industry     

Corrosion studies on electrochemically deposited PANI and PANI/epoxy coatings on mild steel in acid sulfate solution

The corrosion behavior of mild steel and mild steel covered by electrochemically deposited (a) polyaniline (PANI) film, (b) epoxy coating and (c) PANI/epoxy coating system in 0.1 M sulfuric acid solution were investigated by electrochemical impedance spectroscopy (EIS). Electrochemical deposition of PANI film was performed from aqueous solution of 0.5 M sodium benzoate and 0.1 M aniline at constant current density of 1.5 mA cm⁻². Epoxy coatings on mild steel and mild steel modified by PANI film were deposited at constant voltage. It was shown that thin PANI film had provided good corrosion protection of mild steel in 0.1 M sulfuric acid solution, and could be used for modification of mild steel prior to epoxy coating deposition. The increased corrosion protection of mild steel by PANI/epoxy coating system in the same solution was obtained.     

Carbon nanotubes/polyaniline nanocomposite coatings: Preparation,rheological behavior,and their application in paper surface treatment

Conventional cellulosic paper, rendered electro‐conductive, may hold considerable promise for diversified applications in such areas as electro‐magnetic interference shielding and energy storage. Here, an electro‐conductive cellulosic paper was prepared by surface application of multi‐walled carbon nanotubes (MWCNTs)/polyaniline (PANI) nanocomposites onto a conventional base paper. MWCNTs/PANI nanocomposites were prepared by in situ polymerization of aniline with different contents of MWCNTs and used as electro‐conductive filler for the fabrication of electro‐conductive surface‐coated paper. The achieved MWCNTs/PANI nanocomposites exhibited a core‐shell structure, as evidenced by TEM. Effects of feeding ratios of MWCNTs on the rheological behavior of nanocomposite coatings, as well as the mechanical properties and electrical conductivity of surface‐coated paper were studied. Results revealed that the rheological behavior of the nanocomposite coatings showed strong dependence on the MWCNTs content. Moreover, both the electro‐conductivity and mechanical properties of surface‐coated paper were improved as a function of surface application of MWCNTs/PANI nanocomposites, particularly, in presence of an optimum content of MWCNTs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46329.     

A new smart coating of polyaniline–SiO2 composite for protection of mild steel against corrosion in strong acidic medium

Organic coating approaches for corrosion protection with inherently conducting polymers have become important because of restriction on the use of heavy metals and chromates in coatings due to their environmental problems. The present work is directed towards the synthesis of polyaniline (PANI) and polyaniline–SiO₂ composites (PSCs) by chemical oxidation polymerization in the presence of phosphoric acid and evaluation of synthesized PANI and PSCs for protection of mild steel from corrosion in a strong aggressive medium (i.e. 1.0 mol L^–1 HCl). A suitable coating with PSC was formed on mild steel using epoxy resin by the powder coating technique. A comparative study of the corrosion protection efficiency of mild steel coated with PANI and PSC in 1.0 mol L^–1 HCl solution was evaluated using the Tafel extrapolation, chrono‐amperometry and weight loss methods. The PSC coating showed that a significant reduction in the corrosion current density reflects the better protection of mild steel in an acidic environment. Higher protection efficiency up to 99% was achieved by using PSC‐coated mild steel at 6.0 wt% loading of PSC in epoxy resin. The coating performance and corrosion rate of mild steel were investigated by using immersion of polymer‐coated mild steel in 1.0 mol L^–1 HCl for 60 days and indicated that PSC‐coated mild steel showed better performance from corrosion than PANI in an acidic medium.© 2012 Society of Chemical Industry     

Epoxy curing by polyaniline (PANI) – Characterization and self-healing evaluation

Polyaniline (PANI) was synthesized by chemical oxidative polymerization of aniline dissolved in aqueous phosphoric acid. The polymer was characterized by UV–Visible spectroscopy (UV–Vis), thermal gravimetric analysis (TGA) and Fourier transform infrared spectroscopic (FTIR) techniques. Hardener free epoxy coating was formulated with 10% PANI. The curing process of epoxy resin by PANI was analyzed using FTIR and a suitable mechanism of curing was suggested. The corrosion protective performance of conventional polyamide cured epoxy and PANI cured epoxy coating on steel has been assessed in 3% NaCl by electrochemical impedance spectroscopy (EIS). The self-healing property of the PANI cured epoxy coating on steel in 3% NaCl was studied by scanning vibrating electrode technique (SVET).     

Preparation and performance of new antifouling resins containing BIT group

New acrylate grafting epoxy antifouling resins containing benzoisothiazoline ketone (BIT) group were successfully synthesized, and their structures and performances were determined. Experimental data indicated that the new acrylate grafting epoxy antifouling resins have a strong bonding to the cured epoxy resin coating through chemical reaction and self-stratifying. And the paint prepared by using the new resin as matrix has excellent self-polishing and antifouling properties. Especially its antifouling period could be modified by changing the weight ratio of the usage of the mixed monomers and epoxy resin in the preparing process of the acrylate grafting epoxy antifouling resins.     

Conducting polymer based hybrid nano-composites for enhanced corrosion protective coatings

Hybrid composite coatings containing zinc oxide (ZnO) and polyaniline (PANI) as nano-additives dispersions were prepared with poly(vinyl acetate) (PVAc) as the major matrix. The steel plates dip-coated with these formulations were tested for corrosion protection by immersion in saline water over long periods. The Tafel plots for the determination of open circuit potential (OCP) and corrosion current (I_corr) were recorded. The coatings containing both ZnO and PANI showed improved corrosion resistance as compared to the single component coating. The I_corr values of PVAc–ZnO–PANI are found to be two-order magnitude lower than that of PVAc and PVAc–ZnO coatings. The results are explained on the basis of enhancement in barrier properties due to nano-particulate additives in PVAc–ZnO–PANI film together with the redox behaviour of PANI and protective oxide layer formation near the substrate.     

Synthesis and characterization of composites of polyaniline and polyurethane‐modified epoxy

A toughened, semiconductive polyaniline/polyurethane (PANI/PU)‐epoxy nanocomposite was prepared using a conductive polymer, PANI, and a PU prepolymer‐modified diglycidyl ether of bisphenol A (DGEBA) epoxy. The formation of a nanostructure was confirmed by Fourier transform infrared spectroscopy and SEM. The mechanical properties of the composites were evaluated and compared with those of the corresponding matrix. The improvement in impact strength of the composites (especially in the PANI/PU(PPG2000)‐epoxy system) was explained after fracture surface analysis using SEM. DSC and TGA studies indicated that the thermal properties of these composites were comparable to those of DGEBA epoxy. A conductivity in the range 10^?9–10^?3 S cm^?1 was obtained, depending on the testing frequency (10³–10⁷ Hz) and the PANI content incorporated. Copyright © 2006 Society of Chemical Industry     

Sol-gel synthesis and antibacterial study on BC/ZnO/TiO2 nanocomposite treated by DC glow discharge plasma

Nanocomposite material of bamboo charcoal (BC), zinc oxide (ZnO), and titanium dioxide (TiO₂) has prepared via sol–gel method. The synthesized nanocomposite surface was modified by a DC glow discharge plasma treatment. Characterization methods such as BET, SEM, XRD, FTIR, UV, and EDAX are utilized to examine the presence of all the three materials and their combination structure. The combined and plasma-modified surface structure of the bamboo charcoal/zinc oxide/titanium dioxide (BC/ZnO/TiO₂) nanocomposite has shown by microscopic images in step by step. The phase structure of the prepared nanocomposite has been identified by X-ray diffraction and the crystalline size of the composite falls between 20 and 30 nm. The antibacterial behavior of the prepared nanocomposite was assessed through disk diffusion plate method and best antibacterial performance was observed. The metal oxides and plasma treatment increased the property of the synthesized nanocomposite and also the results gave extended results compared to BC/ZnO and BC/TiO₂ in all formats.     

Effect of polyaniline surface modification of carbon nanofibers on cure kinetics of epoxy resin

Polyaniline (PANI) “nanograss” was grown on carbon nanofibers (CNFs). The cure behavior of an epoxy resin with and without unmodified CNFs or PANI modified CNFs was studied by means of non‐isothermal and isothermal differential scanning calorimetry (DSC). CNFs accelerated the reaction of epoxy and diamine. PANI surface modification further increased the reaction rate and the extent of reaction. An autocatalytic cure kinetic model was used to fit the reaction curves. It was found that activation energies of the epoxy reaction decreased in the presence of CNFs and PANI modified CNFs. The observed catalytic effect of CNF and PANI surface coating can be very useful for low temperature cure of large epoxy composite products. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

PANI-chitosan-TiO2 ternary nanocomposite and its effectiveness on antibacterial and antistatic behavior of epoxy coating

A straightforward approach has been developed for fabricating antibacterial and antistatic epoxy coatings by using polyaniline-chitosan modified TiO₂ ternary nanocomposite. This nanocomposite was synthesized through the following steps. First, chitosan was grafted onto the TiO₂ nanoparticles and then final nanocomposite was prepared via solution polymerization of aniline. Electrical conductivity measurement revealed that nanocomposite with 7.5 wt % of the modified TiO₂ nanoparticles has noticeably higher conductivity compared to polyaniline. Evaluating the coatings' antibacterial property indicated epoxy coatings with the content of ternary nanocomposite show significant bactericidal activity against Gram-positive bacteria and have acceptable antibacterial action against Gram-negative ones. Also, obtained results showed that the ternary nanocomposite would greatly decrease coatings' surface resistivity and when nanocomposite content is about 2 wt % surface resistivity is about 3 × 10⁷ Ω sq⁻¹. On the contrary, the coating with nanocomposite loading exhibits improved thermal and mechanical performance compared to the coating made of neat epoxy. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47629.     

Effect of Metal Doped Zinc Oxide Nanorods on Photoelectrical Characteristics of ZnO/Polyaniline Heterojunction

The n-type vertically aligned metal doped ZnO nanorods (NRs) and p-type proton acid doped polyaniline (PANI) inorganic/organic heterojunction diodes have been fabricated. Aluminium (Al) and iron (Fe) doped ZnO NRs were grown on seed ZnO layer on fluorine doped tin oxide coated glass substrates by high temperature chemical bath deposition method. The elemental analysis using EDAX confirm doping of Al and Fe in ZnO. The morphology of doped ZnO nanorods and ZnO/PANI heterojunction exhibit well defined uniform nanorod arrays and interface between nanorods and polyaniline matrix respectively. The dark current–voltage curves confirmed the rectifying diode like behaviors of the heterojunctions, whereas under illumination, the junction revealed good sensitivity to UV and visible range with increased current densities. The highest ideality factor and lowest barrier height was found for FeZnO/PANI heterojunction under dark and under light compared to that of ZnO/PANI, AlZnO/PANI. This research is innovative with respect to low cost synthesis of efficient and sensitive hybrid p–n junction diodes and possibly serves as the building blocks for future optoelectronic applications.     

Corrosion protection of mild steel by nano-colloidal polyaniline/nanodiamond composite coating in NaCl solution

The polyaniline/nanodiamond (PANI/ND) nanocomposite coating was synthesized on mild steel via electrochemical polymerization using cyclic voltammetry technique. The ultrasonic irradiation was used for effectively dispersing ND particles in electropolymerization solution. The prepared nanocomposite films were found to be nano-colloidal, and very adherent with low porosity. X-ray diffraction and FTIR techniques confirmed the intercalation of the nanoparticles in PANI matrix. The corrosion performance of the coatings was investigated in 3.5% NaCl solution by electrochemical impedance spectroscopy (EIS), polarization, and salt spray methods. The obtained results showed that the presence of ND particles significantly enhanced the corrosion protection performance of the PANI films in corrosive medium. EIS and polarization measurements indicated that the coating resistance and corrosion resistance values for the PANI/ND nanocomposite coating were much higher than that of pure PANI-coated electrode. Also, the results obtained revealed that the protection efficiency of PANI/ND-coated mild steel is achieved about 90% after 3 days. The porosity in PANI/ND nanocomposite coating is almost 18 times lower than that of the PANI coating.