Preparation and characterisation of silica/epoxy hybrid nanocomposite coatings containing boehmite nanoparticles for corrosion protection

Abstract

A hybrid silica/epoxy nanocomposite film containing boehmite nanoparticles has been developed in this work through the sol–gel method to protect AA2024 alloy from corrosion. The hybrid sols were prepared by copolymerisation of 3-glycidoxypropyltrimethoxysilane, tetraethylorthosilicate and aluminium isopropoxide. The films were prepared by dip coating technique. The morphology and the structure of the hybrid sol–gel films were studied by scanning electron microscopy and atomic force microscopy. The corrosion protection properties of the films were investigated by potentiodynamic scanning and electrochemical impedance spectroscopy. The results indicate that the presence of the boehmite nanoparticles in hybrid structure of the silica/epoxy films, highly improved the corrosion protection performance of the coating system.     

Effect of polymeric structure on the corrosion protection of epoxy coatings

Two epoxy resins, EP and EPA, with similar backbone structure but different water affinity, was obtained by curing o-cresol novolac epoxy resin with phenol novolac resin and phenol novolac acetate resin, respectively. By using these two resins, the effect of the polymeric structure on the corrosion protection of the coatings was studied. The free volume in EPA is larger than that in EP as demonstrated by room-temperature density measurement and positron annihilation, while water sorption of EPA is only half of that of EP. Therefore, water affinity of the resin is more important in determining water sorption of the resin than free volume. The cross-sectional area of water passage at coating/metal interface (A_w) was estimated using the electrochemical impedance spectroscopy and compared with that in the resin matrix (A_cs). It was found that, for EPA, A_w is much less than A_cs, which suggests a significant narrowing of water passage at the coating/metal interface. This narrowing of water passage at coating/metal interface due to the formation of a hydrophobic layer can greatly improve the corrosion protection of the coating.     

Evaluation of corrosion protection of carbon black filled fusion-bonded epoxy coatings on mild steel during exposure to a quiescent 3% NaCl solution

Carbon black (CB) was mixed with fusion-bonded epoxy (FBE) coatings to generate a series of formulations with 0.5-4% by weight of carbon black. The degradation of these FBE coatings on mild steel exposed to a quiescent 3% NaCl solution was monitored using electrochemical impedance spectroscopy (EIS). The experimental results showed that the electrochemical behaviour of coated systems changed dramatically when the CB concentration reached 3% by weight. This phenomenon was relevant to the formation of the percolation regime in the coating, at which a sharp drop in the electrical resistance of the coating was achieved by the generation of a continuous conducting network. A comparison of the protective properties of the FBE coatings filled with various CB loadings, along with the inspection of view underneath the coatings, indicated that the protective performance of the FBE coating was significantly improved when the CB loading exceeded the threshold concentration. This conclusion was confirmed by the results obtained from Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) measurements.     

Sol-gel silica coatings on ZE41 magnesium alloy for corrosion protection

Silica coatings have been applied on the surface of ZE41 magnesium alloy following the organic sol-gel route and the dip-coating technique. Three different concentrations of sol solution and two densification temperatures of the coating (400 °C and 500 °C) were used to optimize the compaction of the coatings and as a result reach the corrosion protection of the metallic substrate tests in 3.5 wt.% NaCl aqueous solution. Crack-free coatings with thickness in the 2-3 μm were obtained on the ZE41 magnesium alloy. The combination of high alkoxide concentration in the sol-gel formulation, and the high sintering temperature (500 °C) leads to coating (D500) with the optimal physical barrier against the corrosion process. This coating was capable of resisting more than 7 days in contact with the aggressive electrolyte suffering minor corrosion degradation. A corrosion mechanism for each of the tested specimens has been proposed.     

The adhesion properties and corrosion performance of differently pretreated epoxy coatings on an aluminium alloy

The influence of various blends of hexafluorozirconic-acid (Zr), polyacrylic-acid (PAA) and polyacrylamide (PAM) pretreatment on the performance of an epoxy coated aluminium substrate was investigated and compared to that of a so-called chromate/phosphate conversion coating (CPCC).Adhesive-strength of epoxy coated substrates was evaluated using pull-off and tape tests. Salt spray, humidity chambers and EIS were employed to characterize corrosion performance of coated substrates with different initial surface pretreatments. Among the Zr-based formulations, PAA/Zr and PAA/PAM/Zr showed the best adhesion strength, while the later revealed a good corrosion performance as well. However, CPCC pretreated sample was still superior in these aspects.     

Corrosion protection of 1008 carbon steel by hybrid coatings

Abstract

Potentiodynamic polarisation curves have been used to evaluate the corrosion performance of 1008 carbon steel coated with hybrid (inorganic-organic) and mixed oxide coating systems deposited by dip coating. Several coatings have been prepared by the sol-gel method, using metallic alkox ides, such as tetraethylorthosilicate, aluminium isopropoxide, and zirconium propoxide, and polymers like allyl methacrylate (AMA) and polymethylmethacrylate (PMMA), together with zirconium dioxide (ZrO₂) and silicon and aluminium oxides (SiO₃-Al₂O₃). The aqueous test solutions included hydrochloric acid (HCl), sodium chloride (NaCl), and sulphuric acid (H ₂SO₄) at various concentrations (0·1, 0·5, and 1M). Scanning electron microscopy was used to examine the coatings following testing. The results have shown that SiO₂-Al₂O₃ based coatings are not beneficial for corrosion protection in HCl, but are of value in the other aqueous media. In 1·0M HCl, the best protection was offered by a hybrid SiO₂-ZrO₂-poly(methylmethacrylate-allyl methacrylate) (P(MMA-AMA)) coating. In NaCl, the best results, were generally obtained with SiO₂-Al₂O₃ and SiO₂-ZrO₂-P(MMA-AMA) coatings. Similarly, in H₂SO₄, the best results were generally displayed by the SiO₂-Al₂O₃ and SiO₂-ZrO₂-P(MMA-AMA) coatings. The corrosion behaviour of the coatings is discussed in terms of the integrity and stability of the film.     

Corrosion protection properties of lacquer coatings on steel modified by carbon black nanoparticles in NaCl solution

Nanometer carbon black (CB) grafted with polyvinyl alcohol was obtained by surface modification, and its size was about 60 nm. In the ultrasonic field, the composite lacquer coatings with different contents of CB nanoparticles were prepared by mechanical agitation. Electrochemical impedance spectroscopy (EIS), anodic polarization curves, immersion measurements and salt fog tests were used to evaluate the corrosion performances of the composite coatings applied on steel in NaCl solution. It was observed that composites coatings with 1 wt% CB nanoparticles reduced drastically the corrosion rate of steel.     

Incorporation of an indole-3 butyric acid modified clay in epoxy resin for corrosion protection of carbon steel

In the present work, indole-3 butyric acid (IBA) was inserted between montmorillonite clay platelets by cation exchange. The clay treated with the organic compound (IBA-modified clay) was then dispersed in an epoxy resin at a low concentration (2 wt.%). IBA was chosen to act both as an inhibitor and an adherence promoter. The effect of the IBA-modified clay on the microstructure and on the protective properties of the epoxy coating deposited on carbon steel was evaluated by a thermostimulated-current (TSC) method and by electrochemical impedance spectroscopy (EIS). The TSC measurements showed the specific action of IBA-modified clay which decreased the molecular mobility of the polymer chain by comparison with the pure epoxy. Impedance measurements corroborated the role of the modified clay on the barrier properties of the coating which remained high as a function of exposure time in a 0.5 M NaCl solution. The corrosion resistance of the carbon steel coated with the epoxy resin containing IBA-modified clay was significantly higher than that obtained with the clear coat. Polarization curves plotted in the presence of an artificial defect demonstrated the inhibitive role of IBA at the carbon steel/coating interface. The good adherence of the coating was seen during salt spray test.     

Conducting polyaniline based paints on low carbon steel for corrosion protection

Conducting polyaniline powder was synthesized chemically and paints containing conducting polyaniline powder were applied on low carbon steel samples. The conducting polyaniline powder was characterized by UV-Visible absorption spectroscopy and the morphology of paint coating on low carbon steel was studied by scanning electron microscopy. The corrosion protection performance of the coating was evaluated by using potentiodynamic polarization techniques and electrochemical impedance spectroscopy. It has been found that the 2 wt % polyaniline-hydrochloric acid based paint coating offers maximum corrosion protection to low carbon steel in chloride medium.     

Novel zinc‐rich epoxy paint coatings with hydrated alumina and carbon nanotubes supported polypyrrole for corrosion protection of low carbon steel: Part II: Corrosion prevention behavior of the hybrid paint coatings

Utilization of various types of multi‐walled carbon nanotubes (MWCNTs) in zinc‐rich paints (ZRPs) is presented addressing percolation and porosity related phenomena of traditional ZRPs. Hybrid paint coatings were formulated with 3.21 wt% polypyrrole (PPy) deposited alumina‐MWCNT inhibitor particles (PDAMIPs) and 70 wt% zinc contents. Corrosion protection behavior of the hybrid coatings was investigated by electrochemical impedance spectroscopy (EIS), glow‐discharge optical emission spectroscopy (GD OES), X‐ray photoelectron spectroscopy (XPS), and FT‐Raman spectroscopy. Immersion and salt‐spray chamber tests gave evidence of improved galvanic protection and barrier nature of the hybrid coatings over the conventional ZRPs, whereas inhibited zinc corrosion and ignorable steel corrosion took place besides lower degradation of the binder. Zinc‐rich hybrid paints with either high relative amount of polyelectrolyte‐modified or low proportion of functionalized MWCNTs afforded enhanced corrosion prevention. This result is partly attributed to the nanotube volume fractions around the threshold of infinite cluster formation contributing to electrical percolation and galvanic action of the hybrids. Experimental results are discussed in a broader context on the basis of structure related findings of the PDAMIPs (described in Part I) and in the light of recent literature data. From the newly developed inhibitor particles, some of them are respected as worthy additives for application in hybrid coatings featuring high performance corrosion prevention functionality.     

Polybenzoxazine/SiO2 nanocomposite coatings for corrosion protection of mild steel

A series of nanocomposite coatings (PBS) consisting of silane functional polybenzoxazine (PB-TMOS) and SiO₂ nanoparticles were developed for corrosion protection of mild steel. The influence of silica content on corrosion resistance of PBS coatings was investigated by electrochemical measurements. The surface chemistry of nanoparticles and its effect on morphology of the PBS coating was also studied utilizing Fourier Transforms Infrared Spectroscopy, ²⁹Si Nuclear Magnetic Resonance and Scanning Electron Microscopy analyses. The results indicate that the presence of the covalent bond between nanoparticles and PB-TMOS, greatly improves the interfacial interactions at the polymer/filler interfaces resulting in a better corrosion performance.     

Assessment of graphene oxide/epoxy nanocomposite as corrosion resistance coating on carbon steel

Graphene and its derivatives are new materials with unique properties. In recent years, various studies about the nanocomposites based on graphene oxide (GO) have been carried out. However, the electrochemical properties of nanocomposite coatings based on GO materials have not been widely studied. In this study, GO/epoxy nanocomposite coatings were prepared by incorporation of different amounts of GO nanosheets into the epoxy matrix via mechanical agitation and sonication process. The dispersion of GO nanosheets in matrix was analysed by optical microscopy, transmission electron microscopy and Fourier transform infrared. The anticorrosive properties of these nanocomposite coatings were investigated by electrochemical impedance spectroscopy tests. Results showed that the corrosion protection of coatings was improved by addition of GO into the coatings material. Furthermore, the best corrosion resistance was achieved in 0·25 wt-%GO/epoxy nanocomposite coatings.     

The effect of thermo-mechanical treatment on The pitting corrosion of reinforcing carbon steel bars

Steel reinforcing rods with varying amounts of cold work and carbon concentrations (0.06 to 0.45% C) exposed in soil embankments has shown various degrees of pitting corrosion. To understand this pitting process, laboratory investigations on residual stresses, microstructures and potentiodynamic cyclic polarization were undertaken. Analysis of residual stresses in the steels indicated low value of compressive stresses in hot rolled steels and high value of tensile stresses in the cold worked counterparts. Hot rolled steels displayed a slightly better pitting corrosion resistance than cold worked samples which is consistent with the above internal stress pattern. No definite correlation was obtained between the percentage of carbon in the steels and pitting susceptibility. An attempt has been made to define the role of the complex steel-soil system for pitting corrosion behavior.     

The effect of phosphonates on the corrosion of carbon steel in heat-supply water

The effect of phosphonates used in Russian heat-power engineering on the corrosion of carbon steel in deaerated delivery water at 90°C is studied. It is shown that introduction of phosphonates reduces the susceptibility of steel to local corrosion. A zinc complex of hydroxyethylidenediphosphonic acid (OEDP-zinc) is the most effective inhibitor of the anodic reaction. Original Russian Text ? Yu. V. Balaban-Irmenin, A.M. Rubashov, N.G Fokina, 2006, published in Zashchita Metallov, 2006, Vol. 42, No. 2, pp. 146–149.     

Novel zinc‐rich epoxy paint coatings with hydrated alumina and carbon nanotubes supported polypyrrole for corrosion protection of low carbon steel: Part I: Inhibitor particles and their dispersions

In part 1 of this work, preparation, structure, spectroscopic, and electrochemical characteristics of the polypyrrole (PPy) deposited alumina/multi‐walled carbon nanotubes (MWCNTs) inhibitor particles (PDAMIPs) are presented. TEM observations evidenced uniform deposition of thin PPy film on the functionalized nanotubes, whereas co‐deposition of PPy and polystyrene sulfonic acid (PSS) lead to thick polymer coverage on hydrated alumina. Modification with polymer complexes resulted in moderately dispersed PDAMIPs, which is due to the various degrees of aggregation and coalescence. FTIR revealed compact and dense PPy structure on the functionalized MWCNTs while it was not the case on alumina and the PSS modified nanotubes. Closer interaction of PPy with the MWCNTs resulted in enhanced charge mobility, whereas greater electroactivity and reversibility of PPy were noted to samples containing functionalized nanotubes and low amount of PSS. Rheological study verified moderate micron‐scale dispersity and the modification caused various degrees of aggregations of the PDAMIPs. These were recognized to be valid in the suspensions at a solid phase concentration with component contents similar to the corrosion tested hybrid coatings. Rheological percolation of the nanotubes (with anisotropic factor of ～100) was confirmed at volume fractions of 3.30 × 10^?3 and 6.0 × 10^?4 which were under the dilute/semi‐dilute boundary type theoretical and experimental thresholds. This is related to the extensive interconnection of the nanotube‐supported filaments. Thus, overlapping of the nanotubes should contribute to the electrical percolation thereby galvanic corrosion prevention function of the zinc‐rich hybrid coatings, which is discussed in the 2nd part.     

Effect of plasma nitriding of electroplated chromium coatings on the corrosion protection C45 mild steel

Plasma nitriding is a promising posttreatment technique to create a nitride layer on electroplated chromium coatings for improving their corrosion resistance. In the present study, the effects of plasma nitriding on the corrosion properties of electroplated chromium/C45 mild steel were investigated using electrochemical characterization. The chromium plated samples were nitrided using a pulsed direct current glow discharge in an NH₃ atmosphere. The polarization curve measurement results showed that the plasma nitrided samples exhibited more positive corrosion potentials (E_corr), smaller corrosion currents (I_corr), and evident passivation when compared with unnitrided chromium plating/substrate system. The high value of E_corr and low value of I_corr imply an improvement of the corrosion resistance of the coating/substrate system after plasma nitriding.