Self-healing and anticorrosive properties of Ce(III)/Ce(IV) in nanoclay–epoxy coatings

The self-healing and anticorrosion effects of cerium nitrate in epoxy–clay nanocomposite coatings systems were studied. Different amounts of cerium (III) were added to epoxy–montmorillonite clay composites and the nanocomposite coatings were prepared and applied on cold rolled steel panels. Ultrasonication was applied to disperse the nanoclay into the epoxy cerium nitrate composition. Electrochemical impedance spectroscopy (EIS) was used to study the self-healing and anticorrosion behaviors of the coatings. The structure of the dry coating and the protective mechanism of the pigments in the coating were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) analysis and field emission electron microscopy (FESEM). Transmission electron microscopy (TEM) illustrated the separation of clay layers which interacted with the epoxy resin. Electrochemical impedance data indicated that the epoxy cerium (III)–montmorillonite nanocomposite coatings were superior to the epoxy coatings in corrosion protection properties. The self-healing behavior of such coatings was due to the presence of cerium nitrate that could be released at the defects within the coating and hindered the corrosion reactions at the defective sites. It was shown that the best corrosion protection was achieved with nanocomposite coatings containing 4 wt% clay and 2 wt% cerium nitrate.     

Formulation and study of corrosion prevention behavior of epoxy cerium nitrate–montmorillonite nanocomposite coated carbon steel

Nanocomposite coatings which were applied on carbon steel panels based on epoxy cerium nitrate–montmorillonite (MMT) were synthesized and formulated. Nanoparticles were incorporated into epoxy resin by mechanical and sonication processes. The state of dispersion, dissolution, and incorporation were characterized by optical microscopy, sedimentation tests, X-ray diffraction, and transmission electron microscopy. To investigate anticorrosive properties of nanocomposite coatings, electrochemical impedance spectroscopy and salt spray tests were employed. The experimental results showed that epoxy cerium nitrate–MMT nanocomposite coatings were superior to the neat epoxy in corrosion protection effects. In addition, it was observed that the corrosion protection of nanocomposite coatings was improved as the clay loading was increased up to 4–2 wt% cerium nitrate.     

The effect of organosilane on corrosion resistance of epoxy coating containing cerium nitrate

Structure and corrosion resistance behavior of epoxy coating containing cerium nitrate in different amounts of γ-glycidoxypropyltrimethoxysilane (γ-GPS) were investigated. Corrosion resistance ability of coating systems was characterized by using electrochemical impedance spectroscopy and polarization techniques. Also atomic force microscopy was used to evaluate dispersion of cerium nitrate in the presence of γ-GPS. Furthermore, the effect of γ-GPS on flexibility of coatings was studied by using the cupping test. Increment of 10?wt.% of γ-GPS into the coating formulation led to the superior dispersion of cerium nitrate and also highest corrosion protection performance.     

Corrosion study of hybrid sol–gel coatings containing boehmite nanoparticles loaded with cerium nitrate corrosion inhibitor

To improve the corrosion protection of sol–gel derived hybrid silica/epoxy coatings containing boehmite nanoparticles, inorganic corrosion inhibitor was introduced into the coating via encapsulation in the nanoparticles. The morphology and chemical structure of the deposited films were studied by Scanning Electron Microscopy (SEM) and Fourier Transformed Infra-red Spectroscopy (FT-IR). The anticorrosion and self-healing properties of the coatings were evaluated by Electrochemical Impedance Spectroscopy (EIS). The high corrosion resistance performance of such coatings is due to the presence of encapsulated cerium nitrate corrosion inhibitor that can be released at the defects within the coating, hindering the corrosion reactions at defective sites.     

Electrospun protective self‐healing coatings for light alloys: A better understanding of the intrinsic potential of the technology

Polymeric coating systems exhibit high potentiality to provide an effective barrier against corrosion of metallic surfaces. However, these coatings can lose their protective characteristics because of their high susceptibility to damage. Thus, the addition of corrosion inhibitors is desirable and considered as an alternative route for active corrosion protection. In the present work, eco‐friendly electrospun coatings of poly(vinyl alcohol) (PVA) loaded with cerium salts have been deposited onto aluminium 6082 alloy. Two different precursors of cerium (III) (i.e., cerium nitrate and cerium acetylacetonate) were added to the electrospinning solutions and the effectiveness of the resulting nanofibrous coatings was evaluated for the healing of generated defects. The microstructural features of the electrospun coatings have been investigated by scanning electron microscopy, infraredspectroscopy, and thermal analysis. Tensile tests were performed to assess the mechanical properties of the different fibrous coatings. The electrochemical behavior of both intact and damaged coatings was evaluated in 3 wt % NaCl solution by means of electrochemical impedance spectroscopy. All the deposited PVA coatings loaded with cerium(III) salts showed remarkable corrosion resistance. In the case of artificially damaged coatings, a self‐healing effect, which stops the development of the corrosion process and provides a significant recovery of the corrosion resistance, has been observed only for coatings loaded with cerium III acetylacetonate. The release of cerium from damaged PVA fibers has been demonstrated by means of inductively coupled plasma mass spectrometry. The observed self‐healing effect has been ascribed to the formation of cerium hydroxide on the defective zone, which hindered the corrosion process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42728.     

Corrosion study of hybrid sol–gel coatings containing boehmite nanoparticles loaded with cerium nitrate corrosion inhibitor

To improve the corrosion protection of sol–gel derived hybrid silica/epoxy coatings containing boehmite nanoparticles, inorganic corrosion inhibitor was introduced into the coating via encapsulation in the nanoparticles. The morphology and chemical structure of the deposited films were studied by Scanning Electron Microscopy (SEM) and Fourier Transformed Infra-red Spectroscopy (FT-IR). The anticorrosion and self-healing properties of the coatings were evaluated by Electrochemical Impedance Spectroscopy (EIS). The high corrosion resistance performance of such coatings is due to the presence of encapsulated cerium nitrate corrosion inhibitor that can be released at the defects within the coating, hindering the corrosion reactions at defective sites.     

SiAlON–epoxy nanocomposite coatings: Corrosion and wear behavior

In this study, epoxy powder as a matrix was combined with different contents of silicon–aluminum–oxygen–nitrogen (SiAlON) nanoparticles using a planetary ball mill. Pure epoxy and nanocomposite powders were applied on the surface of plain carbon steel components by the electrostatic spraying method. Curing of the coatings was done in an oven or microwave for the appropriate time. The coating structure and morphology of the SiAlON nanoparticles were studied by scanning electron microscopy and transmission electron microscopy, respectively. The corrosion properties of the coatings were assessed by immersion, Tafel polarization, and electrochemical impedance spectroscopy tests in 3.5% NaCl solution. The results show that addition of 10 wt % SiAlON nanoparticles markedly increases the corrosion resistance of epoxy coatings. Thus, it can be inferred that the corrosion rate of these coatings is 15 to 18 times lower than that of pure epoxy samples and 8 to 11 times lower than coatings with 20 wt % SiAlON. The higher corrosion resistance of nanocomposite coatings can be attributed to the barrier properties of SiAlON nanoparticles. The tribological performance of the coatings was studied with the pin‐on‐disk test. The results of wear testing show that the samples containing 10 wt % SiAlON provide about five times more wear resistance than pure ones and about two times more than coatings with 20 wt % SiAlON. However, the coefficient of friction for nanocomposite coatings is reduced about 50% compared to the pure sample. Also, the curing process in either regime (oven or microwave) has the same effect on the corrosion and wear properties, and the coatings are completely crosslinked. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43855.     

Nanostructured sol-gel coatings doped with cerium nitrate as pre-treatments for AA2024-T3: Corrosion protection performance

Nanostructured hybrid sol-gel coatings doped with cerium ions were investigated in the present work as pre-treatments for the AA2024-T3 alloy. The sol-gel films have been synthesized from tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) precursors. Additionally the hybrid sol was doped with zirconia nanoparticles prepared from hydrolyzed tetra-n-propoxyzirconium (TPOZ). Cerium nitrate, as corrosion inhibitor, was added into the hybrid matrix or into the oxide nanoparticles.The chemical composition and the structure of the hybrid sol-gel films were studied by XPS (X-ray photoelectron spectroscopy) and AFM (atomic force microscopy), respectively. The evolution of the corrosion protection properties of the sol-gel films was studied by EIS (electrochemical impedance spectroscopy), which can provide quantitative information on the role of the different pre-treatments. Different equivalent circuits, for different stages of the corrosion processes, were used in order to model the coating degradation. The models were supported by SEM (scanning electron microscopy) measurements.The results show that the sol-gel films containing zirconia nanoparticles present improved barrier properties. Doping the hybrid nanostructured sol-gel coatings with cerium nitrate leads to additional improvement of the corrosion protection. The zirconia particles present in the sol-gel matrix seem to act as nanoreservoirs providing a prolonged release of cerium ions. The nanostructured sol-gel films doped with cerium nitrate can be proposed as a potential candidate for substitution of the chromate pre-treatments for AA2024-T3.     

Effect of the incorporation of montmorillonite-layered double hydroxide nanoclays on the corrosion protection of epoxy coatings

A series of layered double hydroxide (LDH)/montmorillonite (MMT) nanocomposite coating, LDH nanocomposite coating, and MMT nanocomposite coating were successfully prepared. The nanocomposite materials were characterized by X-ray diffraction and scanning electron microscopy (SEM). To understand the effect of MMT and LDH on the corrosion inhibition performance of epoxy resin coatings immersed in 3.5 wt% saline solution at 90°C, electrochemical impedance spectroscopy and an autoclave test were performed on epoxy resin; epoxy resin blended with LDH, MMT, and LDH + MMT (LM) coatings painted on Q345 steel. The metal/coating interfaces were observed by SEM and energy-dispersive spectroscopy. Results showed that addition of LDH and MMT improved the protection properties of the epoxy resin coatings. The corrosion protection of the LM nanocomposite coating was superior to that of the other coatings. This finding can be attributed to the ionic selectivity and barrier effect of MMT and LDH nanoclay platelets dispersed within the composite coatings.     

Study on cerium-doped nano-TiO2 coatings for corrosion protection of 316?L stainless steel

Many methods have been reported on improving the photogenerated cathodic protection of nano-TiO₂ coatings for metals. In this work, nano-TiO₂ coatings doped with cerium nitrate have been developed by sol–gel method for corrosion protection of 316 L stainless steel. Surface morphology, structure, and properties of the prepared coatings were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy. The corrosion protection performance of the prepared coatings was evaluated in 3 wt% NaCl solution by using electrochemical techniques in the presence and absence of simulated sunlight illumination. The results indicated that the 1.2% Ce-TiO₂ coating with three layers exhibited an excellent photogenerated cathodic protection under illumination attributed to the higher separation efficiency of electron–hole pairs and higher photoelectric conversion efficiency. The results also showed that after doping with an appropriate concentration of cerium nitrate, the anti-corrosion performance of the TiO₂ coating was improved even without irradiation due to the self-healing property of cerium ions.     

Synthesis of 3-glycidoxypropyltrimethoxysilane modified hydrotalcite bearing molybdate as corrosion inhibitor for waterborne epoxy coating

Zinc aluminum hydrotalcite intercalated with molybdate (HTM) and modified by 3-glycidoxypropyltrimethoxysilane (HTM-GS) was prepared and incorporated into a waterborne epoxy coating. The synthesized HTM-GS was characterized by FTIR, XRD, SEM, and TEM. The inhibitive action of HTM-GS on carbon steel was evaluated using electrochemical measurement and SEM/EDX analysis. The corrosion protection of the waterborne epoxy coating containing HTM-GS was evaluated and compared to that of the pure waterborne epoxy coating and the waterborne epoxy coating containing HTM by salt spray test and adhesion measurement. It was shown that the molybdate was intercalated in the hydrotalcite structure and the molybdate contents in HTM and HTM-GS were 16.0 and 13.2 wt%, respectively. The polarization curves obtained on the carbon steel electrode showed that HTM and HTM-GS are anodic corrosion inhibitors, and their inhibition efficiencies at concentration of 3 g/l were 92.0 and 94.7%, respectively. Additionally, HTM and HTM-GS at concentration of 0.5 wt% improved corrosion resistance and adhesion of waterborne epoxy coatings. Surface modification by 3-glycidoxypropyltrimethoxysilane ameliorated the dispersion of HTM in epoxy matrix and the effect of HTM on protection properties of waterborne epoxy coating.     

Improving the corrosion protection properties of organically modified silicate–epoxy coatings by incorporation of organic and inorganic inhibitors

Organically modified silicate (ORMOSIL)–epoxy coatings were formed on aluminium alloy 2024-T3 in order to protect the substrates from corrosion. Organic and inorganic compounds, all known for their corrosion inhibition ability, were incorporated into the polymer matrix for the improvement of the corrosion resistance. The ORMOSIL–epoxy coatings were deposited via the dip-coating process. The properties of the coatings were investigated after 24 h of curing at 90 °C. The morphology of the coatings was examined by scanning electron microscopy (SEM). Their composition and structure were investigated by Fourier transform infrared spectroscopy (FT-IR) and energy dispersive X-ray analysis (EDX). The corrosion resistance of these coatings was investigated using electrochemical impedance spectroscopy (EIS). The results showed that the most effective corrosion protection ability was provided by the inorganic inhibitors and that an important role can be attributed to the cation in the nitrate salt.     

Synergic enhancement of the anticorrosion properties of an epoxy coating by compositing with both graphene and halloysite nanotubes

The aim of this research was to improve the corrosion resistance of metal surfaces with polymer coatings. Both graphene and halloysite nanotubes (HNTs) were introduced together into the epoxy resin coating for the enhanced barrier protection of the metallic surface. The anticorrosion behaviors of different coatings were comparatively evaluated by the potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and neutral salt spray (NSS) tests. The potentiodynamic polarization curves showed that the coating containing 0.5 wt % HNTs and 0.8 wt % graphene (H05G08EP) together had the most positive corrosion potential and the minimum corrosion current density. The EIS results revealed that graphene endowed the composite coatings with excellent electrochemical performance for anticorrosive purposes. The NSS tests indicated that H05G08EP endured the longest NSS time. These results suggest that H05G08EP had the best corrosion resistance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47562.     

Influence of the doping agent on the corrosion protection properties of polypyrrole grown on aluminium alloy 2024-T3

The corrosion protection properties of polypyrrole (PPy) electrodeposited onto aluminium alloy 2024-T3 substrates were investigated as a function of the doping agent. We used camphor sulfonic acid (CSA), para toluene sulfonic acid (p-TSA), phenylphosphonic acid (PPA), oxalic acid (OA) and cerium nitrate salt (Ce(NO₃)₃) as doping agents. The resulting coatings have been evaluated towards corrosion protection of aluminium alloy 2024-T3 using electrochemical impedance spectroscopy (EIS). Complementary, scanning electron microscopy (SEM) provided images on the morphology and the thickness of the coatings. The results showed that coatings formed using Ce(NO₃)₃ solution protect the substrate more efficiently compared to the other coatings.     

Effect of ceria and zirconia nanoparticles on corrosion protection and viscoelastic behavior of hybrid coatings

Organic–inorganic hybrid nanocomposite coatings contain inorganic particles that are dispersed in organic phase in nanometric dimensions. Ceria and zirconia colloidal dispersions are uniformly distributed in the epoxy silica-based hybrid nanocomposite by sol–gel method and coated on 1050 aluminum alloy substrate with spin-coating technique. The hybrid sol is prepared by organic–inorganic precursors formed by hydrolysis and condensation of 3-glycidoxypropyltrimethoxysilane and tetraethylorthosilicate (TEOS) in acidic solution using bisphenol A as networking agent and 1-methylimidazole as initiator in the presence of various ratios of ZrO₂ and CeO₂ colloidal nanoparticles. Particle size distribution, surface morphology and inorganic components distribution were determined by scanning electron microscopy (SEM) and EDXA techniques. SEM and Si, Zr, Ce mapping micrographs proved the uniform distribution of nanoparticles in the coatings. Transmission electron microscopy indicated that the nanoparticles dimension stay at the nanoscale level. The glass transition temperature (T _g) and loss properties (damping) of coatings were evaluated by dynamic mechanical thermal analysis. The corrosion protection of the coatings on the 1050 AA substrate was studied by potentiodynamic measurements. The results indicated that by introducing ceria nanoparticles in 1:1 molar ratio to TEOS in coating composition, corrosion protection was improved. However, the simultaneous presence of two nanoparticles (i.e., ceria and zirconia in 1:1 molar ratio) in the coating compositions increased the corrosion protection efficiency up to 99.8 %. The multiple glass transitions and shifting to higher and wide range of temperatures by adding ceria and zirconia nanoparticles indicated a better network interaction between inorganic nanoparticles and organic molecular chains which also led to better corrosion protection of the coating in this composition.     

Eco‐friendly,acrylic resin‐modified potassium silicate as water‐based vehicle for anticorrosive zinc‐rich primers

Potassium silicate binder of zinc‐rich coating was modified by adding water‐based acrylic resin. Several series of coatings containing 5, 10, and 15 wt % of acrylic and acrylic/styrene binders were added to potassium silicate. The coatings were applied on steel and the corrosion resistance of coatings was evaluated by conventional methods such as electrochemical impedance spectroscopy, corrosion potential, salt spray, and scanning electron microscopy. The results indicated that the modification of silicate binder with acrylic and acrylic/styrene led to shortening the curing time, improved corrosion protection, better dispersion of zinc particles, and enhanced salt spray resistance of resultant coatings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40370.     

Electrochemical effects of silane pretreatments containing cerium nitrate on cathodic disbonding properties of epoxy coated steel

In the recent years, silane materials, because of their environmental friendly nature and ease of application have been attended as an alternative for chromate conversion coatings. Different materials were searched for improvement of the efficiency of silane formulation. In this research, pretreatment of carbon steel substrates was carried out using γ-glycidoxypropyl-trimethoxysilane (γ-GPS) as functionalized silane. Cerium nitrate as a corrosion inhibitor material was introduced into the silane material and epoxy resin was applied on the pretreated steel substrates. Effects of the pretreatment on electrochemical properties, cathodic disbondment, dry and wet adhesion strength, and surface morphology of resultant epoxy coating were investigated. Results showed that pretreatment of steel substrate with γ-glycidoxypropyl-trimethoxysilane (γ-GPS) doped with cerium nitrate leads to improvement of cathodic disbondment and also dry and wet adhesion of epoxy coating. Furthermore, this type of pretreatment reduced the disruption of interfacial bonds at the binder/substrate interface. Addition of 2?wt% cerium nitrate into the silane formulation led to the maximum efficiency of resultant coating.     

Effect of cerium concentration on microstructure,morphology and corrosion resistance of cerium–silica hybrid coatings on magnesium alloy AZ91D

The aim of this work was to investigate the effect of cerium concentration on microstructure, morphology and anticorrosion performance of cerium–silica hybrid coatings on magnesium alloy AZ91D. Vinyltriethoxysilane (VETO) and γ-glycidoxypropyltrimethoxysilane (GPTMS) were employed as precursors to prepare sol–gel based silica coating. Cerium nitrate hexahydrate as dopant in five different concentrations was added into the silica coatings. Fourier transform infrared (FT-IR) spectrum analysis, viscosity measurements and scanning electron microscopy (SEM) were employed to characterize the microstructure and morphology of these coatings. It was found that with the increase of cerium concentration, the degree of decomposition of silane chains in the coating network increased. The corrosion resistance of the cerium–silica hybrid coatings was estimated by electrochemical impedance spectroscopy (EIS) measurements and potentiodynamic polarization tests. The results demonstrated that corrosion resistance of coatings initially increases and then decreases as cerium concentration goes up. When the cerium concentration is 0.01 M, corrosion resistance reaches its maximum.     

Thermomechanical and corrosion inhibition properties of graphene/epoxy ester–siloxane–urea hybrid polymer nanocomposites

The effect of graphene on the corrosion inhibition properties of a hybrid epoxy–ester–siloxane–urea polymer was investigated. The weight fraction of graphene was varied from 1 to 2 wt%. Direct current polarization (DCP) and electrochemical impedance spectroscopic (EIS) techniques were used to measure the polarization and coating resistance of the coated aluminum alloy substrate. The grapheme/hybrid polymer composite coatings showed much higher corrosion inhibition property when compared to the neat hybrid polymer coating. An increase in glass transition temperature and rubbery region modulus was also observed for composites containing 1–2 wt.% of graphene. A direct correlation between the rubbery plateau modulus of free standing composite thin films and corrosion resistance of the composite coatings was made, indicating that the corrosion protection mechanism is due to restriction of the polymer chain motion by graphene which causes a decrease in coating permeability.     

A new approach to using submicron emeraldine-base polyaniline in corrosion-resistant epoxy coatings

The present work reports on a new approach to the preparation of special corrosion-resistant epoxy coatings. The aminic hardener of these coatings contained emeraldine-base polyaniline (EB-PANi). The aminic hardener was prepared by dispersion of EB-PANi in 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine employing sonication, centrifuging and submicron filtering methods. The state of dispersion and dissolution of these coating materials, during different stages of preparation, were characterized by optical microscopy and scanning electron microscopy. The corrosion resistances of resulting coatings were measured by electrochemical impedance spectroscopy (EIS) and salt spray methods. As little as 0.5% EB in initial mixture of EB-hardener compositions led to relatively better corrosion protection of resulting coating compared with neat resin coating. Presence of initial 2.5% of EB in the hardener and its processing through our approach resulted in the formulation of an epoxy coating with superior corrosion protection properties.