A room temperature cured sol–gel anticorrosion pre-treatment for Al 2024-T3 alloys

The inherent reactivity of the Al–Cu alloys is such that their use for structural, marine, and aerospace components and structures would not be possible without prior application of a corrosion protection system. Historically these corrosion protection systems have been based upon the use of chemicals containing Cr(VI) compounds. Organic–inorganic hybrid silane coatings are of increasing interest in industry due to their potential application for the replacement of current toxic hexavalent chromate based treatments. In the present study, a hybrid epoxy–silica–alumina coating with or without doped cerium nitrate has been prepared using a sol–gel method. The hybrid coatings were applied by a dip-technique to an Al–Cu alloy, Al 2024-T3, and subsequently cured at room temperature. The anticorrosion properties of the coatings within 3.5% NaCl were studied using electrochemical impedance spectroscopy (EIS), and conventional DC polarisation. An exfoliation test method involving immersion in a solution of 4 M NaCl, 0.5 M KNO₃ and 0.1 M HNO₃ was also used. The cerium nitrate doped sol–gel coating exhibited excellent anticorrosion properties providing an adherent protection film on the Al 2024-T3 substrate. The resistance to corrosion of the sol–gel coating was also evaluated by analysing the morphology of the coating before and after corrosion testing using scanning electron microscopy.     

Exfoliation corrosion of Al–Zn–Mg–Cu–Zr alloy containing Sc examined by electrochemical impedance spectroscopy

The exfoliation corrosion behavior of an Al–Zn–Mg–Cu–Zr alloy containing Sc artificially aged at 120 °C for 24 h is studied by macroscopic observation techniques and electrochemical impedance spectroscopy (EIS) measurements. After 48 h immersion, the blisters start bursting and delamination initiates, along with the appearance of two time constants in the impedance diagrams. According to the simulation by equivalent circuit, the corrosion rate decreases sharply and then reaches a steady state, which is due to the change of the solution pH and oxide layer thickness, as well as the accumulation of corrosion products.     

Corrosion study of Ni/Zn compositionally modulated multilayer coatings using electrochemical impedance spectroscopy

Ni/Zn compositionally modulated multilayer (CMM) coatings were deposited using dual bath technique. Coatings corrosion performance was evaluated using electrochemical impedance spectroscopy (EIS) during extended immersion times up to 48 h. The results of electrochemical impedance spectroscopy showed that Ni/Zn CMM coatings had better corrosion resistance compared to that of the zinc single layer coating. The modified corrosion product which is formed on the Ni/Zn CMM coatings during extended exposure times and also a good barrier effect of the nickel layer against aggressive species in these coatings can be two important reasons for high corrosion performance and so protection performance of the Ni/Zn CMM coatings.     

In situ impedance spectroscopy study of the electrochemical corrosion of Ti and Ti–6Al–4V in simulated body fluid at 25 °C and 37 °C

The corrosion resistance of Ti and Ti–6Al–4V was investigated through electrochemical impedance spectroscopy, EIS, potentiodynamic polarisation curves and UV–Vis spectrophotometry. The tests were done in Hank solution at 25 °C and 37 °C. The EIS measurements were done at the open circuit potential at specific immersion times. An increase of the resistance as a function of the immersion time was observed, for Ti (at 25 °C and 37 °C), and for Ti–6Al–4V (at 25 °C), which was interpreted as the formation and growth of a passive film on the metallic surfaces.     

Impedance spectroscopy studies of electroless Ni–P matrix,Ni–W–P,Ni–P–ZrO2, and Ni–W–P–ZrO2 coatings exposed to 3.5% NaCl solution

Ni–P matrix, ternary Ni–W–P and Ni–P–ZrO₂ coatings, and quaternary Ni–W–P–ZrO₂ coatings were deposited using electroless method from a glycine bath. Their corrosion resistance was evaluated by electrochemical impedance spectroscopy (EIS) for various immersion times in a 3.5% NaCl solution. From among the investigated coatings, the ternary Ni–W–P coatings show the highest resistance to corrosion in the first hour of exposure to the 3.5% NaCl medium. An addition of ZrO₂ adversely affects the performance of both the Ni–P coatings and the Ni–W–P coatings. For all the coatings, including the ones containing tungsten, a marked decrease in pore resistance (R_por) over time is observed. This means that their corrosion resistance and capacity to protect the substrate decline. On the other hand, after 24 h immersion in the 3.5% NaCl solution the Ni–W–P coating shows the highest low‐frequency impedance modulus (|Z|_{f = 0.01 Hz}). As regards corrosion resistance, the Ni–P coatings and the Ni–W–P coatings perform best.     

2-Mercaptobenzimidazole as a copper corrosion inhibitor: Part I. Long-term immersion, 3D-profilometry,and electrochemistry

The high corrosion inhibition effectiveness of 2-mercaptobenzimidazole (MBIH) in 3 wt.% aqueous NaCl solution is reported using long term immersion tests, 3D-profilometry, electrochemical impedance spectroscopy, and potentiodynamic curve measurements. The high corrosion inhibition performance was proven after 180 days of immersion. The impedance spectra were characterized by two time constants relating to charge transfer and finite layer thickness or semi-infinite diffusion of copper ions through the surface layer, therefore Cu corrosion in solution containing MBIH follows kinetic-controlled and diffusion-controlled processes. Moreover, it is shown that MBIH is a mixed-type inhibitor.     

Electrochemical methods study on corrosion of 5% Al–Zn alloy‐coated steel under thin electrolyte layers

The corrosion behavior of a 5% Al–Zn alloy (GF) coated steel was investigated under cyclic wet–dry condition using electrochemical techniques. The wet–dry cycle was conducted by exposure to alternate condition of 1 h immersion in seawater and 7 h drying at ambient temperature. The polarization resistance, R_p of the coating was monitored during the wet–dry cycles by two points AC impedance method and the corrosion potential, E_corr was measured only when the coating was immersed in seawater. Simultaneously, the electrochemical impedance spectroscopy (EIS) of the coating was obtained after it was immersed in different cycles of wet–dry condition. The results obtained by two points AC impedance method had good agreement with those achieved from EIS technique, which proved that the two points AC impedance method was correct and an effective method for atmospheric corrosion study. The monitoring results indicated that the corrosion rate of GF coating firstly increased, then decreased slowly with time, and at last reached a relative steady state with local corrosion under the cyclic wet–dry alternate condition.     

Effects of Ce-containing sol–gel coatings reinforced with SiO2 nanoparticles on the protection of AA2024

A hybrid organic–inorganic self-healing coating for anticorrosive protection of AA2024 was developed through the sol–gel method. Combination of permeability, provided by a methacrylate-silica hybrid matrix, with hardness and density of silica nanoparticles, allowed obtaining a coating material where the diffusion of Ce ions occurred at the same time that an anticorrosive physical barrier was developed. Electrochemical impedance spectra (EIS) on coated samples showed an increase of the impedance modulus at 0.01 Hz as a function of immersion time in a 3.5 wt% NaCl solution. Self-healing effect was verified by impedance fitting through the evolution of resistive and capacitive parameters of the equivalent circuits.     

Electrochemical corrosion behaviors and protective properties of Ni–Co–TiO2 composite coating prepared on sintered NdFeB magnet

In this paper, a protective Ni–Co–TiO₂ composite coating was prepared on the sintered NdFeB magnet by direct current electrodeposition. The surface morphologies, microstructure, and chemical composition of the composite coating were studied using scanning electron microscope (SEM), X‐ray diffraction (XRD), and energy dispersive spectroscopy (EDS), respectively. The surface morphologies and microstructure analysis showed that the composite coating possessed cauliflower‐like grain colonies, and formed face‐centered cubic (fcc) solid solution. The electrochemical corrosion behaviors of the composite coating in 0.5 mol/L H₂SO₄, 0.6 mol/L NaOH, 0.6 mol/L Na₂SO₄, and neutral 3.5 wt% NaCl solutions were evaluated by potentiodynamic polarization measurements and electrochemical impedance spectroscopy (EIS), showing good protection for NdFeB magnet. In order to further investigate the protective properties of the composite coating for NdFeB magnet and the practicability of the composite coating, the long‐term immersion test was carried out in neutral 3.5 wt% NaCl solutions using EIS. The results of long‐term corrosion test showed that the Ni–Co–TiO₂ composite coating could provide long‐term protection in neutral 3.5 wt% NaCl solutions for NdFeB magnet.     

Influence of pH on the deterioration of plasma electrolytic oxidation coated AM50 magnesium alloy in NaCl solutions

The corrosion deterioration process of plasma electrolytic oxidation (PEO) coatings on AM50 magnesium alloy prepared from two different based electrolytes, i.e., an alkaline phosphate electrolyte and an acidic fluozirconate electrolyte, were investigated using electrochemical impedance spectroscopy (EIS) in a 0.1 M NaCl solution with pH of 3, 7 and 11, respectively. It was found that the PEO coating formed in alkaline phosphate electrolyte, which was composed mainly of MgO, suffered from rapid chemical dissolution and lost its protection capability very quickly in acidic NaCl solution (pH 3). The chemical dissolution of this PEO coating was retarded in neutral NaCl solution (pH 7) and the corrosion damage was localized in this environment. On the other hand, in the alkaline NaCl solution (pH 11), the MgO coating underwent only slight degradation. The PEO coating produced in acidic fluozirconate electrolyte, the failure was marked by the flaking-off of the large areas of coating in acidic NaCl solution (pH 3). However, in the neutral and alkaline NaCl solutions, the coating underwent only a slight degradation without any observable corrosion damage in the 50 h test. The results showed that the deterioration process of PEO coated magnesium alloy was governed mostly by the pH of NaCl solution and it was also strongly related to the microstructure and composition of the PEO coatings.     

Application of embedded sensors in the thermal cycling of organic coatings

A standard Air Force polyurethane topcoat/epoxy chromate pigmented primer system was characterized using the thermal cycling method. This method is an accelerated test method for organic coatings that involves exposing the coating to alternating room temperature and elevated temperature cycles under constant immersion. Electrochemical properties were monitored using electrochemical impedance spectroscope for the total topcoat/primer system, the inner layer of primer, and the outer layer of the topcoat. The individual layers were monitored using platinum sensors embedded between the layers. Characterization of a system comprising of two layers of the epoxy chromate pigmented primer was also performed using EIS monitoring, and embedded sensors. The systems were cycled between room temperature, and set temperatures up to 80 °C. The barrier property of the topcoat and the bulk resistance of the primer were consistent with Arrehenius behavior. The results obtained were consistent with the intended design of the polyurethane topcoat and chromate primer with the former providing the significant barrier protection, whereas the primer providing the passivating chromate to the metal/coating interface. Analysis of the EIS data obtained from the sensor with an equivalent circuit decoupled the bulk primer properties from the metal/coating interface properties.     

Electrochemical corrosion behavior of electroless Ni–P coating in NaCl and H2SO4 solutions

Electrochemical corrosion behavior of electroless Ni–P coating in NaCl and H₂SO₄ solutions were studied by potentiodynamic polarization curves and electrochemical impedance spectra techniques, as well as the corrosion morphology was characterized. The results indicate that electroless Ni–P coating with about 25 µm is stable in 30 days immersion in NaCl solution. Although it was corroded with prolonged immersion days, the corrosive medium has not penetrated through the coating. During the H₂SO₄ concentration ranging from 5 to 10%, the corrosion current density of electroless Ni–P coating increased due to the intensified anodic dissolution process; in 15% H₂SO₄ solution, electroless Ni–P coating shows obvious anodic passivation effect.     

Corrosion behavior of lanthanum-based conversion coating modified with citric acid on hot dip galvanized steel in aerated 1 M NaCl solution

Rare earth conversion coating is one of the most promising substitutes to the toxic chromate coating. The corrosion resistance of lanthanum conversion coating modified with citric acid on hot dip galvanized (HDG) steel was investigated in aerated 1 M NaCl solution by means of electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. Equivalent circuits were subsequently developed from the measurements to elucidate the corrosion behavior of the coating. The surface morphology of the lanthanum conversion coating was observed by scanning electron microscopy (SEM), and the chemical composition of the coating was characterized by energy dispersive spectroscopy (EDS). The results showed that the corrosion process of the modified lanthanum conversion coating consisted of three stages. The overall corrosion resistance of the coating was excellent.     

EIS study of the corrosion behaviour of zinc-based coatings on steel in quiescent 3% NaCl solution. Part 1: directly exposed coatings

The possibilities offered by the EIS technique for studying the progress of corrosion in several types of galvanised coatings were investigated. Corrosion tests were performed in a 3 wt.% NaCl aqueous solution, at approximately neutral pH, without stirring and in contact with the air. A tendency was seen towards an electrochemical overestimation of the corrosion values of essentially pure zinc and Zn-5%Al (Galfan) coatings compared with the gravimetric reference values. In contrast, the opposite tendence was revealed with the Zn-10%Fe (Galvanneal) coating. These deviations have made it necessary to use empirical values of the constant B of the Stern-Geary equation. The approximately linear progress of the attack with immersion time suggests a slight barrier effect of the corrosion products layer.     

Corrosion behaviour of Zn–Al–Mg coated steel sheet in sodium chloride-containing environment

Conventional hot-dip galvanised zinc coated (Z) and novel hot-dip galvanised Zn–Al–Mg alloy coated (ZM) steel sheet samples with a coating thickness of 7 μm each were exposed to standardised salt spray test and cross-sections of the corrosion samples were analysed by using SEM and EDS. On Z corrosion proceeds very fast and the steel substrate is attacked even after 100 h of exposure. ZM samples showed a different behaviour. The entire metallic ZM coating is converted into a stable, adherent aluminium-rich oxide layer, which protects the steel substrate against corrosive attacks. This layer is the main reason for the enhanced corrosion resistance of the ZM coating in sodium chloride-containing environment.     

Effect of heat treatment on H2S corrosion of a micro-alloyed C–Mn steel

The H₂S corrosion resistance of a C–Mn pipeline steel with three different microstructures has been evaluated using electrochemical techniques with a 3% wt. NaCl solution at 50 °C. Microstructures included martensite, ferrite, and ferrite + bainite. Electrochemical techniques included potenthiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), and electrochemical noise (EN) measurements. Most of the tests lasted 24 h. All techniques showed that the highest corrosion rate corresponded to the steel with a martensitic microstructure; up to one order of magnitude higher than the corrosion rate for steels with a ferritic + bainitiic microstructure, whereas the steel with the ferritic microstructure showed the lowest corrosion rate. EIS tests showed that the corrosion process was under charge transfer control, whereas EN results indicated that the three steels exhibited a clear tendency towards a localized type of corrosion. However, for longer immersion times, the steel with a martensitic microstructure tended to exhibit a mixture of uniform and localized attack. Results were discussed in terms of grain size, grain boundary energy, amount and distribution of particles found in each steel.     

Long-term anticorrosion behaviour of polyaniline on mild Steel

Anticorrosion performances of polyaniline emeraldine base/epoxy resin (EB/ER) coating on mild steel in 3.5% NaCl solutions of various pH values were investigated by electrochemical impedance spectroscopy (EIS) for 150 days. In neutral solution (pH 6.1), EB/ER coating offered very efficient corrosion protection with respect to pure ER coating, especially when EB content was 5-10%. The impedance at 0.1 Hz of the coating increased in the first 1-40 immersion days and then remained constant above 10⁹ Ω·cm² until 150 days, which in combination with the observation of a Fe₂O₃/Fe₃O₄ passive film formed on steel confirmed that the protection of EB was mainly anodic. In acidic or basic solution (pH 1 or 13), EB/ER coating also performed much better than pure ER coating. However, these media weakened the corrosion resistance due to breakdown of the passive film or deterioration of the ER binder.     

Preparation, corrosion and structural properties of Cu–Ni multilayers from sulphate/citrate bath

Potentiostatic electrodeposition was used to produce Cu–Ni multilayer by two-wave pulse plating technique from sulphate/citrate electrolyte at pH 4. Cyclic voltammetry studies provide information about the deposition potential. The compositions of multilayers were studied using X-ray fluorescence (XRF). Electrochemical corrosion studies of the deposited multilayer on copper were studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The surface of the layer having smooth, small grain and compact structure was confirmed by scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis. The face centered cubic lattices are present in the Ni–Cu multilayer and this is confirmed by the X-ray diffraction (XRD) data. The multilayer structures have better corrosion resistance than the base substrate.     

Localized coating failure of epoxy-coated aluminium alloy 2024-T3 in 0.5 M NaCl solutions: Correlation between coating degradation, blister formation and local chemistry within blisters

The role of pH on the nature and rate of the degradation of epoxy coatings on AA2024-T3 panels and subsequent corrosion of the substrate during immersion in NaCl solutions was investigated. In acidic solutions both blister formation and growth are rapid. Blisters become very large (≈1 cm) and new blisters appear to form for a certain time after exposure. Often very small (∼0.1 mm) clear blisters surround these large blisters. Enhanced blister formation is due to irreversibly increased permeability of the coating for chloride ions and protons, the formation of more defect sites within the coating, and the weakening/dissolution of the oxide layer in low pH environments. In neutral pH solutions, coatings fail by forming one, or at most two, active blisters (red in color) within a few days of immersion with the time-to-failure dependent upon coating quality and thickness. Blister growth is a very slow process, and blister diameters rarely exceed a few millimeters even after several weeks. The accumulation of corrosion product within the blister slows down the corrosion rate and blister growth. The chloride concentration in the occluded solutions within the blister is significantly increased over the bulk concentration, and the pH is often in the acidic range. From electrochemical measurements it can be concluded that the anodic and cathodic reactions are confined to the blister and its immediate surroundings, rather than involving more of the surface over which the coating is intact. Based on corrosion morphology it is concluded that replated copper contributes to the overall cathodic reaction.     

CeO2-filled sol–gel coatings for corrosion protection of AA2024-T3 aluminium alloy

Hybrid organic–inorganic sol–gel-matrices, with up to 20 wt.% incorporated ceria nanoparticles, have been employed as coatings for an AA2024-T3 aluminium alloy. The morphology of the coatings and associated nanoparticles has been examined by conventional and high-resolution transmission electron microscopy, revealing a relatively uniform distribution of 5 nm size nanoparticles across the coating thickness. Electrochemical studies indicate a general beneficial effect of incorporation of ceria nanoparticles, although the performance of the coated alloy depends on the nanoparticle content. Electrochemical polarisation behaviour revealed that the coating decreased the anodic current density by about seven orders of magnitude compared with the uncoated alloy, with high breakdown potentials in chloride-containing solution. Accelerated salt spray testing showed that corrosion in an artificial scratch is blocked most efficiently by high ceria contents, whereas general corrosion is inhibited effectively with comparatively low ceria contents. Electrochemical impedance spectroscopy indicated degradation of the barrier properties of coatings with increased amounts of incorporated nanoparticles. Assessment of the abrasion and scratch resistance, and hydrophobicity also revealed additional beneficial functional properties of the coatings containing nanoparticles.