Polyaniline inhibition of filiform corrosion on organic coated AA2024-T3

Dispersions of the polyaniline emeraldine salt (ES) of paratoluene sulphonic acid (PAni-pTS) effectively inhibit filiform corrosion (FFC) affecting polyvinyl butyral (PVB) coated AA2024-T3 aluminium alloy. An in-situ scanning Kelvin probe (SKP) technique is used to study the effect of systematically varying PAni-pTS volume fraction (?_pa) on FFC initiation and propagation. For ?_pa < 0.15, there is no evidence of FFC inhibition and E_corr values recorded for the intact coated aluminium (E_intact) remain similar to those measured for unpigmented PVB. At ?_pa ≥ 0.15, a marked rise in E_intact is observed, FFC propagation rates decrease and significant oxide growth is observed at the coating-metal interface. For emeraldine base (PAni-EB)-containing coatings, there is no evidence of interfacial oxide film formation, no ennoblement of E_intact and minimal inhibition of FFC. Conversely, when a PAni-pTS induced oxide covered surface is re-coated using unpigmented PVB and FFC is initiated as per normal, a substantial reduction in the rate of FFC propagation is observed. It is therefore proposed that inhibition of FFC by PAni-pTS arises principally as a result of the protective nature of the oxide film formed at the metal-coating interface.     

Transitions between pitting and intergranular corrosion in AA2024

The pitting and intergranular corrosion (IGC) behavior of various tempers of AA2024 was investigated in 1 M NaCl. The breakdown potentials associated with pitting or IGC were determined. The breakdown potentials were found to be almost independent of sample orientation for any given temper. Artificial aging had a strong effect on polarization behavior and localized corrosion morphology. The anodic polarization curves of AA2024 in the solution heat treated and water-quenched condition, T3, and T3+ tempers exhibited two breakdown potentials, whereas overaged AA2024-T8, T8+, and solutionized and furnace cooled AA2024 exhibited only one breakdown potential. When two breakdown potentials were observed, the more active one was found to be related to the transient dissolution of S phase Al₂CuMg particles leading to pitting while the noble one was thought to result primarily from initiation and growth of IGC. The breakdown potentials decreased with increasing aging time at 190 °C, and only one breakdown potential was measured for T8 and T8+ tempers. Unlike the T3 temper, no sharp IGC was found for these tempers. Selected granular attack from breakdown of the copper-depleted matrix was believed to be the cause for localized corrosion in the T8 and T8+ tempers. The effect of nitrate and sulfate ions on the localized corrosion behavior was also studied.     

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.     

Role of nanostructure in pitting of Al-Cu-Mg alloys

Aluminium alloys possess a unique combination of strength and low density, which historically have made these alloys ideal for many structural applications. However, addition of alloying elements in appreciable concentrations, in particular Cu and Mg, make Al-alloys inherently susceptible to localised corrosion. In this work, we adopt a bottom-up approach in an attempt to quantify the critical microstructural feature size (viz. precipitate size) that is capable of triggering a cascade of pitting events and eventual degradation of corrosion resistance. This is accomplished by exploiting the well characterised hardening response in a model alloy, Al-1.1Cu-1.7Mg (at.%), for which pitting resistance of the alloy was tracked with aging time and hence microstructural evolution. Corrosion performance and microstructural characterisation were carried out using a combination of electrochemical testing, coupled with high-resolution scanning transmission electron microscopy (HRSTEM) and atom probe tomography (APT). Results indicate, at least for this particular alloy, that second phase features below a critical width of approximately 3 nm can be tolerated from a corrosion perspective. This study has potentially wide consequences in the understanding of aluminium alloy corrosion initiation and the development of highly corrosion resistant aluminium alloys.     

Effects of selected water chemistry variables on copper pitting propagation in potable water

The pit propagation behavior of copper (UNS C11000) was investigated from an electrochemical perspective using the artificial pit method. Pit growth was studied systematically in a range of HCO₃⁻, SO₄²⁻ and Cl⁻ containing-waters at various concentrations. Pit propagation was mediated by the nature of the corrosion products formed both inside and over the pit mouth (i.e., cap). Certain water chemistry concentrations such as those high in sulfate were found to promote fast pitting that could be sustained over long times at a fixed applied potential but gradually stifled in all but the lowest concentration solutions. In contrast, Cl⁻ containing waters without sulfate ions resulted in slower pit growth and eventual repassivation. These observations were interpreted through understanding of the identity, amount and porosity of corrosion products formed inside and over pits. These factors controlled their resistive nature as characterized using electrochemical impedance spectroscopy. A finite element model (FEM) was developed which included copper oxidation kinetics, transport by migration and diffusion, Cu(I) and Cu(II) solid corrosion product formation and porosity governed by equilibrium thermodynamics and a saturation index, as well as pit current and depth of penetration. The findings of the modeling were in good agreement with artificial pit experiments. Malachite, bronchantite, cuprite, nantokite and atacamite corrosion products were both observed in experiment and predicted by the model. Stifling and/or repassivation occurred when the resistance of the corrosion product layer became high enough to lower the pit bottom potential and pit current density such as 10^-5 A/cm² could be attained with thick and dense layer. The ramifications of these findings towards pit propagation characteristics in potable waters will be discussed with improved insight into the roles of Cl⁻ and SO₄²⁻ ions.     

AC and DC studies of the pitting corrosion of Al in perchlorate solutions

The pitting corrosion behaviour of Al in aerated neutral sodium perchlorate solutions was investigated by potentiodynamic, cyclic voltammetry, galvanostatic, potentiostatic and electrochemical impedance spectroscopy (EIS) techniques, complemented by ex situ scanning electron microscopy (SEM) examinations of the electrode surface. The potentiodynamic anodic polarization curves do not exhibit active dissolution region due to spontaneous passivation. The passivity is due to the presence of thin film of Al₂O₃ on the anode surface. The passive region is followed by pitting corrosion as a result of breakdown of the passive film by ClO₄⁻ ions. SEM images confirmed the existence of pits on the electrode surface. Cyclic voltammetry and galvanostatic measurements allow the pitting potential (E_pit) and the repassivation potential (E_rp) to be determined. E_pit decreases with increase in ClO₄⁻ concentration, but increases with increase in potential scan rate. Potentiostatic measurements showed that the overall anodic processes can be described by three stages. The first stage corresponds to the nucleation and growth of a passive oxide layer. The second and the third stages involve pit nucleation and growth, respectively. Nucleation of pit takes place after an incubation time (t_i). The rate of pit nucleation (t_i⁻¹) increases with increase in ClO₄⁻ concentration and applied step anodic potential (E_s,a). EIS measurements showed that at E_s,a < E_pit, a charge-transfer semicircle is obtained. This semicircle is followed by a Warburg diffusion tail at E_s,a > E_pit. An attempt is made to compare the values of E_pit and E_rp obtained through different methods and to determine the factors influencing these values in each particular method.     

A review of the effects of benzotriazole on the corrosion of copper and copper alloys in clean and polluted environments

A continuing challenge in materials design is the achievement of high operational efficiency through improvements in performance criterion, particularly its service life-time characteristics. Benzotriazole (BTAH) has now been in use for many years for the protection of copper and copper alloys against various forms of corrosion. In this review, the chemistry of BTAH and theories regarding its mode of action are summarized. Also, a survey of the reported work in both clean and polluted environments is documented. More interestingly, the adverse effect of BTAH on the corrosion of Cu and Cu alloys in sulfide polluted environments is introduced.     

Corrosion protection of AA2024-T3 using rare earth diphenyl phosphates

Existing corrosion protection technologies for aluminium alloys utilising chromates are environmentally damaging and extremely toxic. This paper presents a preliminary investigation into rare earth diphenyl phosphates as new environmentally benign corrosion inhibitors. Full immersion weight loss experiments, cyclic potentiodynamic polarisation measurements and Raman spectroscopy were used in this study. Results show cerium diphenyl phosphate (Ce(dpp)₃) acts as a cathodic inhibitor, decreasing cathodic current density and E_corr by passivating cathodic intermetallic particles on the alloy surface. Mischmetal diphenyl phosphate (Mm(dpp)₃) acts a mixed inhibitor, shifting E_corr to more noble values, decreasing cathodic current density, increasing the breakdown potential and suppressing pitting.     

Processable polyaniline-HCSA/poly(vinyl acetate-co-butyl acrylate) corrosion protection coatings for aluminium alloy 2024-T3: A SVET and Raman study

Scanning vibrating electrode technique (SVET) analysis of processable polyaniline-HCSA/poly(vinyl acetate-co-butyl acrylate) coated on to aluminium alloy 2024-T3 exhibited strong interaction between the polymer coating and the underlying metal. A scribed defect in the coating surface resulted in rapid oxidation of the exposed metal within a coating defect while the overlying polymer coating underwent both reduction and dedoping. Under the conditions investigated no protective oxide was observed to form. Raman spectroscopy of the polymer surface confirmed that dedoping was the dominant process which was accompanied by a clear reduction of the emeraldine salt form of the coating to the leucoemeraldine base form within the defect. This coating/metal interaction was observed to be dependant of the proximity to an artificial defect, initially yielding a more reduced material in close proximity to the coating defect, providing evidence of an electrochemical interaction between the polyaniline co-polymer system rather than a barrier effect.     

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.     

Multifunctional,environmental coatings on AA2024 by combining anodization with sol-gel process

The present work proposes the development of multifunctional composite coatings on AA 2024 by combining anodization and sol-gel process. To render the surface of AA 2024 with maximum corrosion resistance, eco-friendly citric-sulfuric acid (CSA) electrolyte with low sulphur content was used for anodization at 20 V for a duration of 30 min. The obtained anodized layer was porous. Ambient curable hybrid sol-gel coating with 8-hydroxy quinoline (8-HQ) as corrosion inhibitor was used as a sealant for the porous anodized layer to enhance the corrosion resistance with self-healing properties. Surface pre-treatments were carried out using sand blasting and alkaline etching to ensure high surface activity prior to anodization. The surface morphology and chemical composition of samples with and without coatings were characterized by field emission scanning electron microscopy (FESEM) and energy dispersive X-ray spectroscopic analysis (EDX). Adhesion strength and wettability of the coatings were measured by tape adhesion test and water contact angle analysis respectively, which revealed excellent binding strength and hydrophobic nature. The corrosion resistance of the coatings was evaluated using electrochemical impedance spectroscopic (EIS), potentiodynamic polarization and salt spray tests. The results revealed improved corrosion resistance of anodized + 8-HQ sealed AA2024. Moreover, when the coated samples were scribed and exposed to the corrosive medium, the SEM/EDX mapping confirmed presence of corrosion inhibitors at the location of the defect, thereby confirming the self-healing property. Hence, the proposed system is a chromium-free, environment friendly multifunctional system exhibiting excellent self-healing corrosion protection and can be a promising substitute for chromic acid anodization.     

Electrochemical studies of the pitting corrosion of tin in citric acid solution containing Cl

The electrochemical behavior of a tin electrode in citric acid solutions of different concentrations was studied by electrochemical techniques. The E/I curves showed that the anodic behavior of tin exhibits active/passive transition. Passivation is due to the formation of Sn(OH)₄ and/or SnO₂ film on the electrode surface. Addition of NaCl to citric acid solution, enhances the active dissolution of tin and tends to breakdown the passivity at a certain breakdown potential. Cyclic voltammetry and galvanostatic measurements allow the pitting potential (E_pit) and the repassivation potential (E_rp) to be determined. Potentiostatic measurements showed that the overall anodic processes can be described by three stages. The first stage corresponds to the nucleation and growth of a passive oxide layer. The second stages involve pit nucleation and growth and third stage involve repassivation. The impedance spectrum of pure Sn is found to consist of three intersecting capacitive semicircles at the high and medium frequencies with an inductive loop at low frequencies. The capacitive semicircles occurring at the high and medium frequency are due to the dielectric properties of surface oxide film and dissolution of underlying metal, respectively. The inductive loop at low frequencies results from Cl⁻ adsorption at the pitting region. By increasing the potential the pitting corrosion and the fractal dimension of surface due to pitting increase.     

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.     

Electro-assisted preparation of dodecyltrimethoxysilane/TiO2 composite films for corrosion protection of AA2024-T3 (aluminum alloy)

Thin films of organosilanes have been successfully used as the alternative to toxic chromate coatings for surface pretreatment of metals and alloys. To further improve their corrosion performance, in the present work nano-scaled TiO₂ particles were added to the dodecyltrimethoxysilane (DTMS) films coated onto AA2024-T3 substrates, by using either the dip-coating or the cathodically electro-assisted deposition process. The obtained composite films were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), water contact angle measurements, Fourier transform reflection-absorption IR (FTRA-IR) and electrochemical impedance spectroscopy (EIS). The results show that these two techniques (nanoparticles incorporation and the electro-assisted deposition) both facilitate the deposition process of silane films, giving thicker deposit and higher coverage surface along with higher roughness and hydrophobicity, and thereby improve their corrosion resistance. Moreover, the corrosion performance of silane films is further improved by the combined use of nanoparticles modification and electro-assisted deposition.     

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.     

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.     

Role of intermetallic phases in localized corrosion of AA5083

The presence of intermetallic inclusions very often plays a crucial role for the susceptibility of different aluminium alloys to localized corrosion attack. The intimate details of localized corrosion of 5083 aluminium alloy have been studied in the present work. Local techniques such as scanning Kelvin probe force microscopy, in situ atomic force microscopy, scanning electron microscopy coupled with energy dispersive spectroscopy were used to investigate the mechanisms and the kinetics of localized corrosion attack. The importance of iron-rich and Mg₂Si intermetallic phases in the initiation of corrosion processes is demonstrated in the paper.The Mg₂Si phase has a potential lower relatively to the matrix. Moreover, the high reactivity of magnesium leads to the dissolution and consequently to the fast dealloying of these intermetallics. However, hydroxide (Mg(OH)₂ and SiO₂·nH₂O) deposits formed during corrosion act as an additional diffusion barrier hindering the deep propagation of pits.The iron containing intermetallics have the potential higher with respect to the aluminum matrix playing the role of effective cathodic centers for oxygen reduction causing anodic polarization and pitting in the surrounding alloy matrix. Dealloying of such intermetallics with subsequent iron enrichment was also revealed. Pitting initiation seems to be statistical and independent of the composition of Fe-rich intermetallics. However, the active growth of the pits prevents initiation of localized corrosion attack in nearby sites. A new pit can start to grow only when a neighbor one becomes passivated.     

Inhibition of copper corrosion in acidic pickling solutions by N-phenyl-1,4-phenylenediamine

Inhibition of copper corrosion by N-phenyl-1,4-phenylenediamine (NPPD) has been investigated in de-aerated, aerated, and oxygenated aqueous 0.50 M HCl solutions by using potentiodynamic polarization, potentiostatic current-time, electrochemical impedance spectroscopy, and weight-loss measurements, along with scanning electron microscopic (SEM) and energy dispersive X-ray (EDX) experiments. Potentiodynamic polarization measurements showed that the NPPD molecules significantly decrease cathodic, anodic, and corrosion currents in all these solutions. Potentiostatic current-time measurements as well as SEM and EDX investigations of the copper surface revealed that NPPD suppresses the copper dissolution current due to its adsorption on the copper surface as a Cu(I)-NPPD complex. Impedance measurements also supported the results obtained from both the potentiodynamic and potentiostatic experiments. The inhibition efficiencies measured from polarization, electrochemical impedance spectroscopy (EIS), and weight-loss experiments are all internally consistent with each other. These results together showed that NPPD is a good mixed-type inhibitor for copper corrosion in all solutions studied.     

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.     

1,2,3-苯并三氮唑铜缓蚀剂的研究进展

苯并三唑(BTAH)是一种非常有效的铜及其合金的缓蚀剂。到目前为止有许多关于BTAH缓蚀作用的研究,但其缓蚀机制仍然不为所知。对BTAH的缓蚀研究作出了总结,以便为进一步研究和开发新的高效缓蚀剂提供依据。