A rapid screening multi-electrode method for the evaluation of corrosion inhibitors

A method is described for the rapid screening of water-soluble corrosion inhibitors, which involves a fixed potential being applied between identical electrodes while immersed in an inhibitor solution. The current flowing between the electrodes is measured and the electrochemical response of the anodic and cathodic reactions, with and without the inhibitor, is then compared. The incorporation of nine pairs of metallic wires (Al, AA2024, AA7075, Fe, mild steel, SS316, Mg, Mg-AZ31 and Zn) into a single assembly enables the effect of inhibitors on different metals to be assessed rapidly. The technique is sensitive to both anodic and cathodic inhibition mechanisms and can provide information on the concentration dependency of inhibitors.This paper provides an electrochemical analysis of the method and demonstrates its application using several soluble chemical species (potassium dichromate, cerium nitrate, sodium vanadate, sodium diphosphate, sodium octanoate) on AA2024-T3 and mild steel at 10⁻² and 10⁻⁴ M and correlates the results with those obtained by conventional potentiodynamic polarization analysis. The errors in the approach were higher for poor inhibitors, however, efficient corrosion inhibitors have decreased experimental errors, thus, ensuring that promising inhibitor candidates are not overlooked.     

Cerium cinnamate as an environmentally benign inhibitor pigment for epoxy coatings on AA 2024-T3

An environmentally friendly inhibitor, cerium cinnamate (CeCin), was studied as an additive to an epoxy coating. The effects of corrosion inhibition on AA 2024-T3 provided by cerium cation and cinnamate anion were investigated by electrochemistry impedance spectra (EIS) and polarization tests. It was found that cerium ion and cinnamate group have synergistic inhibiting effects. The EIS results show that CeCin is an effective inhibitor pigment for improving the corrosion resistance of epoxy coatings on AA2024-T3, as reflected by the much higher coating resistance than that of the blank epoxy coating. The inhibiting effect of CeCin during the onset of corrosion in defects of the epoxy coating was verified using scanning vibrating electrode technique (SVET), which is in agreement with the EIS results.     

Silane and epoxy coatings: A bilayer system to protect AA2024 alloy

This work has proved that a good combination of a simple and fast metal pre-treatment, followed by the deposition of a thin layer of an organic–inorganic silane coating and further layer of epoxy coatings, are able to protect the aluminium alloy AA2024-T3 against corrosion in high concentrations of NaCl solution. The alloy AA2024 is one of the most employed aluminium alloy in structural applications due to its good mechanical properties. However, AA2024 alloy series commonly presents galvanic corrosion due to the rich content of copper element. The influence of different surface pre-treatments, the presence of a silane layer as pre-coating treatment and the influence of phosphonic acids combined with the silane layer on the corrosion protection and adhesion to the aluminium alloy have been examined using accelerated corrosion tests. High roughness and the presence of a pre-coating film between the metal surface and the organic coating were essential for a good protection and resistance to blistering appearance in the surface of AA2024-T3.     

Enhanced corrosion resistance of AA 2024-T3 and hot-dip galvanized steel using a mixture of bis-[triethoxysilylpropyl]tetrasulfide and bis-[trimethoxysilylpropyl]amine

The corrosion resistance of AA 2024-T3 and hot-dip galvanized steel (HDG) was studied after treatment with bis-[3-(triethoxysilyl)propyl]tetrasulfide (bis-sulfur silane), bis-[trimethoxysilylpropyl]amine (bis-amino silane), and their mixture. Electrochemical tests in neutral 0.6 M NaCl as well as scanning electronic microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX) were performed. The results showed that: (1) hydrophilic bis-amino silane did not offer good corrosion protection on either of the metals. This is probably because the bis-amino silane film tends to be positively charged. This promotes ingress of anions like Cl⁻ ions as well as water into the film by electrostatic attraction. As a result, corrosion readily proceeds at the interface. (2) Hydrophobic bis-sulfur silane performed very well on AA 2024-T3, but failed on HDG. The failure here stems from non-uniform film coverage on HDG owing to an insufficient wetting of bis-sulfur silane solution on the Zn oxide on HDG. Local corrosion initiates at defective sites which are poorly covered by the silane film. (3) A bis-sulfur/bis-amino mixture at the ratio of 3/1 greatly enhanced the corrosion resistance of both AA 2024-T3 and HDG. This substantial improvement is achieved by selectively overcoming the major shortcomings of the individual silanes.     

Characterization of hybrid sol–gel coatings doped with hydrotalcite-like compounds to improve corrosion resistance of AA2024-T3 alloys

The inhibition effect of hydrotalcite addition to hybrid sol–gel coatings applied on AA2024-T3 alloy was evaluated. Hydrotalcite belongs to the anionic clay family with wide applications, most of them based on its anion exchange capacity due to its double layered structure. In this work hydrotalcite (HT) powder was prepared by the classical co-precipitation method using magnesium and aluminum nitrates as precursors. Different weight percentages (1, 5 and 10%, w/w) of hydrotalcite with Mg/Al ratio of 2.5 were added to hybrid sols prepared by copolymerization of 3-Glycydoxypropyltrimethoxysilane (GPTMS) and tetra-n-propoxyzirconium (TPOZ). The sol–gel coatings were deposited by dip-coating method on AA2024-T3 substrate. Scanning electron microscopy (SEM) and mechanical profilometry measurements revealed the heterogeneous particle sizes and the distribution of the agglomerates. Hydrotalcite additions significantly increased the bond strength between metal and coating, according to pull-off test results.The corrosion performance was evaluated by the salt spray fog chamber test and by Electrochemical Impedance Spectroscopy (EIS). The results showed a marked improvement of the corrosion resistance on the aluminum alloy when HT was added to the hybrid sol–gel coating. This positive effect was more evident at higher weight percentages of hydrotalcite.     

The influence of pH on corrosion inhibitor selection for 2024-T3 aluminium alloy assessed by high-throughput multielectrode and potentiodynamic testing

This paper complements our recently published work on the development of a high-throughput scanning technique for corrosion inhibitors named multielectrode. The multielectrode set-up, fully described in the previous work, combines nine pairs of different metals in a single multi-metal electrode configuration. In the working procedure a fixed potential is applied between identical metallic electrodes while immersed in an inhibitor solution, without the use of a reference electrode. The current flowing between the electrodes is measured and the combined electrochemical response of the anodic and cathodic reactions, with and without inhibitor, is then characterized. The methodology allows approximately 30 electrochemical experiments to be performed per hour, the rapid identification of inhibitors able to protect different metals, and the rapid detection of the optimal inhibitor concentration.The present work evaluates the influence of solution pH on the anticorrosion performance of three different inhibitors (CeCl₃, Ce(dbp)₃ and K₂Cr₂O₇) on 2024-T3 aluminium alloy (AA2024-T3) by means of conventional potentiodynamic polarization analysis and the multielectrode technique reported previously. The usefulness of the high-throughput multielectrode technique to detect the influence of the solution pH on the anticorrosive performance of different inhibitors has been studied and its correlation with traditional potentiodynamic polarization testing evaluated. The possible reasons for non-correlation between techniques are studied, and those considered important, highlighted. The combined dependence of corrosion inhibition on factors including pH, inhibitor type, and metal cross-contamination was also investigated showing that the multielectrode is a robust technique to detect efficiency changes due to pH variations.     

Electrochemical and morphological assessments of inhibition level of 8-hydroxylquinoline for AA2024-T4 alloy in 3.5% NaCl solution

The corrosion inhibition of AA2024-T4 in 3.5% NaCl solution by 8-hydroxylquinoline (8-HQ) was investigated by potentiodynamic polarisation (PDP), electrochemical impedance spectroscopy and dynamic electrochemical impedance spectroscopy. Experimental results were supported with scanning electron microscopy (SEM), atomic force microscopy and Fourier transform-infrared (FTIR) spectroscopy analysis. It was found that 8-HQ molecules adsorbed on the alloy surface and protected it against corrosion. SEM, energy dispersive spectroscopy, and FTIR results confirm the adsorption of 8-HQ molecules on AA2024-T4. The inhibition efficiency of 8-HQ is found to increase with increase in concentration and the highest concentration studied (0.05 M) offered corrosion inhibition efficiency of 84%. PDP results show that 8-HQ acts as mixed type inhibitor in the studied medium.     

AZ91D镁合金表面不同树脂体系富镁涂层的保护性能

采用划叉浸泡实验,电化学交流阻抗(electrochemical impedance spectroscopy,EIS),开路电位(open circuit potential,OCP)及动电位扫描研究了不同类型的环氧树脂对于AZ91D镁合金的表面的富镁涂层的保护性能的影响。结果表明环氧618-593构成的富镁涂层防护性能较差;环氧6101-TY650制备的富镁涂层可明显改善涂层对破损处镁合金基体的保护作用,但涂层本身长期防护性能较差;环氧618-T31构成的富镁涂层对AZ91D镁合金的防护作用较强,适宜制备镁合金表面的富镁涂层。3种环氧涂料中加入镁粉颗粒制备的富镁涂层均可对缺陷处裸露的AZ91D镁合金基体提供保护,从而延长漆膜的破坏时间。涂层中的镁粉颗粒被激活后,为镁合金的基体提供了一定程度的阴极保护作用,减缓了镁合金基体的腐蚀。     

Electrochemical investigations of polypyrrole aluminum flake coupling

Polypyrrole (PPy) Al flake composite (PAFC) was synthesized by chemical oxidation of pyrrole in the presence of Al flake and was used to formulate a corrosion inhibiting primer. The anticorrosion performance of the PAFC coating for AA 2024-T3 was evaluated by accelerated salt spray, scanning vibrating electrode technique (SVET), galvanic coupling measurement and electrochemical impedance spectroscopy (EIS). The PAFC primer showed an enhanced anticorrosion ability for AA 2024-T3 compared to the Al flake primer and provided cathodic protection for AA 2024-T3 as evidenced by galvanic coupling measurement. A possible corrosion protection mechanism provided by the PAFC and the role of PPy in the formulation were discussed.     

Deposition of hybrid 3-GPTMS's film on AA2024-T3: Dependence of film morphology and protectiveness performance on coating conditions

This paper describes the elaboration of 3-glycidoxypropyltrimethoxysilane (3-GPTMS) films onto AA2024-T3 aluminum alloy for corrosion protection.The dependence of sol–gel morphology on both precipitation under cathodic polarization and nitrate incorporation was investigated via scanning electron microscopy (SEM).Once added into silanization solution, sodium nitrate promoted the reaction of silane condensation and enhanced the film compactness.Electrochemical impedance spectroscopy results (EIS) indicated that doping silane film with NaNO₃ ameliorated its barrier property and protectiveness. Silane films applied onto AA2024-T3 surface by using potentiostatic method, exhibited obviously higher corrosion resistance than those obtained by conventional “dip-coating” method. The resistance of coating is accentuated when not very negative potential was applied.     

Underfilm corrosion on polyurethane-coated aluminum alloy 2024-T3 containing dissimilar metal fasteners

Panels of AA2024-T3 were fastened using Cu and Cu−Ni fasteners, pretreated, and coated with around 25 μm of polyurethane film. The pretreatments were based on typical conversion coating processes. Samples included alkalinecleaned, deoxidized, and conversion-coated. The conversion coatings included chromate and cerium-based conversion coatings. Samples were tested by scribing around the fastener and on the AA2024-T3 (matrix), exposing them to HCl vapor for 15 min, and subjecting them to a filiform corrosion test by exposure to 82% relative humidity at 40±1°C for up to 1000 hr. Inspection showed that the filiform corrosion that developed from a scribe around the fastener was an order of magnitude larger than from a scribe on the matrix (scribe on AA2024-T3). With respect to the surface treatments, the amount of filiform corrosion for scribes on the matrix was greatest on the alkaline-cleaned samples, followed by the deoxidized samples, with the conversion-coated samples performing the best. The amount of filiform corrosion for scribes around the fasteners was highest for the deoxidized sample.     

Improvement of anti-corrosive properties of epoxy-coated AA 2024-T3 with TiO2 nanocontainers loaded with 8-hydroxyquinoline

Epoxy coatings containing TiO₂ nanocontainers were applied on aluminium alloy (AA) 2024-T3 for corrosion protection. The nanocontainers were loaded with the corrosion inhibitor 8-hydroxyquinoline (8-HQ). Epoxy coatings were deposited via the dip-coating process. The morphology of the coatings was examined by scanning electron microscopy (SEM). The composition of the films was determined by energy dispersive X-ray analysis (EDX). Electrochemical impedance spectroscopy (EIS) was employed for the characterization of the corrosion resistance of these coatings. The total impedance values were measured as a function of time exposure in corrosive environment. We observed a continuous increase of the total impedance value with the time of exposure suggesting a possible self-healing effect due to the release of the inhibitors from the nanocontainers. Furthermore, addition of loaded nanocontainers into the coatings leads to the enhancement of the barrier properties of the coatings. Conclusively, we observed an improvement of the performance of the coatings due to the loaded nanocontainers.     

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.     

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.     

Effects of carbon nanotube content on adhesion strength and wear and corrosion resistance of epoxy composite coatings on AA2024-T3

The effects of multiwalled carbon nanotube (MWCNT) content on the adhesion strength and wear and corrosion resistance of the epoxy composite coatings prepared on aluminum alloy (AA) 2024-T3 substrates were evaluated using atomic force microscopy (AFM), blister test, ball-on-disk micro-tribological test and electrochemical impedance spectroscopy (EIS). The adhesion strength of the epoxy composite coatings improved with increasing MWCNT content. Increased MWCNT content also decreased the friction coefficient and increased the wear resistance of the epoxy composite coatings due to improved solid lubricating and rolling effects of the MWCNTs and the improved load bearing capacity of the composite coatings. Finally, EIS indicated that increased MWCNT content increased the coating pore resistance due to a decreased porosity density, which resulted in an increase in the total impedance of the coated samples.     

Effect of doping by corrosion inhibitors on the morphological properties and the performance against corrosion of polypyrrole electrodeposited on AA6061-T6

This paper describes the electrosynthesis of polypyrrole (PPy) onto AA6061-T6 aluminum alloy from a sulfuric acid solution doped with molybdate anions (MoO₄²⁻) or 8-hydroxyquinoline (8HQ) species. These dopant compounds were chosen as they have been proven to be effective in mitigating the corrosion in chloride medium. The protectiveness of PPy coatings incorporating these corrosion inhibitors within the polymer matrix is discussed. The coatings were morphologically characterized via scanning electron microscopy (SEM) and evaluated electrochemically via polarization in 0.5 M NaCl. The results show that doping PPy with molybdates or 8HQ changes its morphological properties and its effectiveness in preventing passivity loss for AA6061-T6 in chloride media.     

A study of the mechanisms of corrosion inhibition of AA2024-T3 by vanadates using the split cell technique

The mechanisms of corrosion inhibition of AA2024-T3 by vanadates were studied in this work using the split cell technique and polarization curves. The electrochemical behavior of clear solutions containing metavanadates and orange solutions containing decavanadates was clearly distinctive. Injection of metavanadates to the cathode side of the different split cell setups greatly reduced the galvanic current, indicating a potent inhibition of the oxygen reduction kinetics. The galvanic current never exhibited a transient current peak, suggesting that metavanadates inhibit AA2024-T3 corrosion by a mechanism that does not involve electrochemical reduction. Injection of metavanadate to the anode side of the different split cells had no effect on the galvanic current. Injection of orange decavanadate to the cathode side of the AA2024-T3 split cell resulted in a large current peak, associated with the electrochemical reduction of decavanadate. However, decavanadates did not impart significant corrosion protection.     

Inhibiting effect of 8-hydroxyquinoline on the corrosion of silane-based sol–gel coatings on AA 2024-T3

This work presents the silane-based sol–gel coatings that prepared by in situ doping 8-hydroxyquinoline as corrosion inhibitor for the protection of AA 2024-T3. The morphology and thickness of the sol–gel coatings were observed by scanning electron microscope (SEM). Immersion tests and electrochemical impedance spectroscopy (EIS) were used to study the corrosion resistance of the blank and 8-hydroxyquinoline doped sol–gel coatings. The results indicate that the addition of 8-hydroxyquinoline effectively improved the corrosion resistance of the sol–gel coatings. The self-healing effect of 8-hydroxyquinoline on the corrosion in the defects of sol–gel coating was assessed by scanning vibrating electrode technique (SVET) and proved by the results of energy-dispersive X-ray spectroscopy (EDS) mapping.     

Impedance study on calcium nitrite as a penetrating corrosion inhibitor for steel in concrete

Penetrating corrosion inhibitors are thought to be able to penetrate through the capillary structure of concrete to reinforcing steel and to reduce the already initiated corrosion of steel. In this work the ability of calcium nitrite to inhibit the chloride induced corrosion of steel was studied. The test protocol was adjusted to simulate the performance of penetrating corrosion inhibitors in concrete structures. Steel samples were first prepassivated in saturated solution of Ca(OH)₂ and then exposed to the same solution with 1% NaCl addition, simulating pore liquid in chloride contaminated concrete. After the initiation of steel corrosion, the first dose of calcium nitrite was added, and then its concentration was gradually increased and the inhibition effect was related to the molar ratio of chloride to nitrite ions [Cl⁻]/[NO₂⁻]. Different rates of the increase in the inhibitor concentration were applied.Electrochemical impedance spectroscopy was used to follow the behaviour of steel at different stages of the corrosion process. The evolution of acquired spectra reflected the initiation of localized corrosion of steel and then the gradual inhibition with increasing concentration of the inhibitor. It was found, that calcium nitrite is able to inhibit the initiated corrosion (pitting) of steel and the optimum inhibitor efficiency was observed for the [Cl⁻]/[NO₂⁻] ratio below 1. The inhibition efficiency was larger, when this value of the [Cl⁻]/[NO₂⁻] ratio was reached in early stages of the corrosion development. Calcium nitrite can be effective as a penetrating corrosion inhibitor for steel in concrete, if it will be present in the sufficient concentration at the steel surface in early stages of the corrosion development.     

Enhancement of Corrosion Performance of Epoxy Coatings by Chemical Modification With GPTMS Silane Monomer

In this paper, commercial epoxy resin was chemically modified by different amounts of 3-glycidoxypropyltrimethoxysilane (GPTMS) monomer using an organotin compound as catalyst, aiming to improve the anti-corrosion performance of epoxy coatings on 2024-T3 aluminum alloy substrate. Electrochemical impedance spectroscopy (EIS) was used to evaluate the barrier properties against water permeation and protectiveness of silane-modified epoxy coatings. The results showed that all the modified coatings presented higher barrier performance and better corrosion performance than pure epoxy coating, which were characterized by higher charge transfer resistance (R _ct) and lower double-layer capacitance (C _dl) at the electrolyte/metal interface. The improvements in corrosion performance and wet adhesion of modified epoxy coatings were also observed by the Machu test and boiling water test, respectively. Interestingly, it was found that the glass-transition temperature (T _g) of silane-modified epoxy coatings decreased only slightly during immersion in 3.5 wt% NaCl solution, in contrast with pure epoxy coating, which was observed to decrease significantly after water permeation. The corrosion performance of epoxy coatings was, thus, improved when the amount of chemically grafted silane monomer increased in the content range investigated in the present work.